EP4136082A1 - Coproduction de monomères, comprenant au moins un monomère d'origine biologique - Google Patents

Coproduction de monomères, comprenant au moins un monomère d'origine biologique

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Publication number
EP4136082A1
EP4136082A1 EP21803766.1A EP21803766A EP4136082A1 EP 4136082 A1 EP4136082 A1 EP 4136082A1 EP 21803766 A EP21803766 A EP 21803766A EP 4136082 A1 EP4136082 A1 EP 4136082A1
Authority
EP
European Patent Office
Prior art keywords
fdca
tpa
oxidation
derivative
monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP21803766.1A
Other languages
German (de)
English (en)
Other versions
EP4136082A4 (fr
Inventor
Andrew Ingram
Erik Hagberg
Chi-Cheng MA
Jessica McClurg
Kenneth STENSRUD
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Archer Daniels Midland Co
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Archer Daniels Midland Co
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Publication date
Application filed by Archer Daniels Midland Co filed Critical Archer Daniels Midland Co
Publication of EP4136082A1 publication Critical patent/EP4136082A1/fr
Publication of EP4136082A4 publication Critical patent/EP4136082A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C61/16—Unsaturated compounds
    • C07C61/20—Unsaturated compounds having a carboxyl group bound to a five-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/14—Monocyclic dicarboxylic acids
    • C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
    • C07C63/26—1,4 - Benzenedicarboxylic acid

Definitions

  • the present invention relates, from one perspective, to processes for making terephthalic acid (TP A) and to the polymers that can be made therefrom. From another perspective, the present invention relates to processes for making TPA’ s biobased analog 2,5-furandicarboxylic acid (FDCA) and to the polymers that can be made therefrom.
  • TP A terephthalic acid
  • FDCA 2,5-furandicarboxylic acid
  • the bio-based monomers, 2,5-furandicarboxylic acid (FDCA) and its dimethyl ester derivative, 2,5-furandicarboxylic acid, dimethyl ester (FDME) are recognized as important starting materials in the production of poly(alkylene furan dicarboxylate) polymers that can substitute for their known, mass-produced petroleum derived analogs, namely poly(alkylene terephthalate) polymers, such as polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • a prominent example of a poly (alky lene furan dicarboxylate) polymers is poly (ethylene furan dicarboxylate), or PEF, obtained by reaction of FDCA or FDME with ethylene glycol.
  • the bio-based polymer (bio plastic) PEF exhibits superior properties in a number of respects, relative to its petroleum derived analog PET, particularly in the area of packaging.
  • blends of PEF and PET can provide improved barrier properties with respect to carbon dioxide and oxygen, prolonging shelf life over that obtained with pure PET and providing an acceptable container for products such as beer that are susceptible to oxidative degradation.
  • Other packaging applications of PEF include films used to manufacture pouches, wrappers, and heat shrink materials having high mechanical strength and recyclability.
  • both FDCA and FDME are useful platform molecules in the production of polyamides, polyurethanes, and polyesters having diverse applications as plastics, fibers, coatings, adhesives, personal care products, and lubricants.
  • the commercial significance of these molecules is evidenced, for example, in a 2004 study by the U.S. Department of Energy, identifying FDCA as one of twelve priority chemicals for establishing the “green” chemical industry of the future.
  • the dehydration product is then oxidized to the desired FDCA, according to a similar Mid-Century type oxidation as employed for the oxidation of p-xylene to make TPA, using a homogeneous catalyst system including cobalt, manganese and bromine components.
  • Certain aspects of the invention relate to the discovery of methods for ameliorating or even eliminating detrimental effects associated with the presence of at least certain species of humins, which are highly colored and generally water- insoluble byproducts of the dehydration of carbohydrates, in processes utilizing such carbohydrates as starting materials in the bio based synthesis of FDCA and derivatives thereof.
  • humins produced in the acid-catalyzed dehydration of carbohydrates having a six-carbon sugar unit tend to consume, or limit the useful capacity of, homogeneous Mid- Century oxidation catalysts.
  • These catalysts have been the most commonly proposed for oxidizing 5-hydroxymethylfurfural (HMF) and/or its derivatives (e.g., ester and/or ether derivatives) that are formed in the upstream dehydration.
  • HMF 5-hydroxymethylfurfural
  • its derivatives e.g., ester and/or ether derivatives
  • co-feeds can be oxidized to form other valuable monomers, in an analogous manner to the oxidation of HMF and/or its derivatives to FDCA.
  • oxidation of both such stabilizing co-feeds and HMF can occur under the same conditions and therefore utilize the same reactor and catalyst system, whether homogeneous or heterogeneous.
  • a particular co-feed of interest is para-xylene, often obtained as a product of crude oil refining, which can be oxidized to terephthalic acid (TP A).
  • certain embodiments are directed to the co-production of monomers through oxidation, such as in the case of co-production of FDCA and TPA.
  • processes for the co-production of FDCA and TPA comprise co-feeding FDCA- forming furanics and para-xylene to an oxidation reactor containing a homogeneous Mid- Century-type oxidation catalyst and reactant oxygen, such that the FDCA-forming furanics and para-xylene are effectively reacted in the same environment, wherein the para-xylene is employed in a sufficient amount as to impart a stabilizing effect (e.g.
  • upstream carbohydrate dehydration is integrated with oxidation of both (i) the dehydration product (e.g., comprising HMF and/or its derivatives) that forms a first monomer and (ii) a stabilizing agent (e.g., para-xylene) that forms a second monomer.
  • the dehydration product e.g., comprising HMF and/or its derivatives
  • a stabilizing agent e.g., para-xylene
  • a co-feed in the oxidation of a carbohydrate dehydration product comprising at least some humins, in which the co-feed partially or completely restores performance (e.g., catalyst activity), relative to a comparative (or baseline) process without co-feed but having the same humins removed from or absent in the dehydration product.
  • performance restoration may be realized using only a minor amount of co-feed (e.g., on a molar basis) relative to the carbohydrate dehydration product, based on the portion thereof that is oxidizable to the desired monomer (e.g., “on path” FDC A- forming furanics).
  • retrofitting can allow for the co production and co-processing of both conventional and biobased monomers with investing only a fraction of the capital and time otherwise needed for construction of a new standalone (“greenfields”) bio-based polyester production facility.
  • a specific type of retrofit may involve, for example, the grafting of a fructose dehydration reactor and associated equipment onto an underutilized or temporarily decommissioned TPA production plant. This can allow for the co-feeding of HMF and/or its derivatives (e.g., ester or ether derivatives, depending on the whether a carboxylic acid solvent or an alcohol solvent is used for forming a solution of the carbohydrate such as fructose that is subjected to dehydration) with para- xylene. Following oxidation of the co-feed, FDCA and TPA may then be provided together in the oxidation product, i.e., as a mixed monomer composition or co-product.
  • HMF and/or its derivatives e.g., ester or ether derivatives,
  • FDCA 2,5-furandicarboxylic acid
  • TPA terephthalic acid
  • the processes comprise contacting an oxidation feed, in the presence of oxygen (e.g., in the presence of an oxygen-containing gas such as air), with an oxidation catalyst to provide the mixed monomer composition.
  • the oxidation feed comprises (i) a dehydration product of one or more carbohydrates (e.g. , fructose) having a 6-carbon sugar unit, and (ii) para- xylene.
  • oxidation catalysts including both homogeneous and heterogeneous catalysts, are capable of being used in a co-oxidation method according to the present invention to produce a mixed monomer composition including both of FDCA and TPA, in addition to the Mid-Century-type oxidation catalysts that have been used commercially for years for producing TPA (and in turn, the esters of TPA).
  • the dehydration and oxidation steps may optionally be combined with a number of additional steps that include color stabilizing, derivatizing (e.g., esterifying), separating, and polymer forming.
  • the polymer forming step may (in relation to the formation of polyesters and copolyesters) itself comprise sub-steps of (i) esterifying or transesterifying, and (ii) polymerizing by polycondensation. These steps and sub-steps may be practiced according to a number of different process configurations, the selection of which would be apparent to one skilled in the art having knowledge of the present disclosure, and in view of the particular feeds being processed and desired end products.
  • One particular embodiment may comprise refining the mixed monomer composition into fractions enriched in the different monomers (e.g., and ideally substantially free of the monomers in which they are depleted), such as into a first, FDCA-enriched fraction and a second, TPA-enriched fraction.
  • fractions enriched in the different monomers e.g., and ideally substantially free of the monomers in which they are depleted
  • Either or both of these fractions may then be subjected to color stabilizing, such as by hydrogenation of color-forming aldehyde byproducts (e.g., 5- formyl-2-furancarboxylic acid (FFCA) that may be present in the FDCA enriched fraction and/or 4-carboxybenzaldehyde (4-CBA) that may be present in the TPA-enriched fraction) or other remediation/purification steps prior to use in a downstream polymer forming step.
  • Another particular embodiment may comprise using remediation/purification steps without separation of the mixed monomer composition into fractions, for example by subjecting the entire mixed monomer composition to color stabilizing, such as by hydrogenation of both FFCA and 4-CBA in the same process stream.
  • the resulting, stabilized composition may then be separated into a stabilized, first fraction (e.g., a stabilized FDCA-enriched fraction) and a stabilized second fraction (e.g., a stabilized TPA-enriched fraction), with the subsequent use of these fractions in separate polymer forming steps.
  • a stabilized, first fraction e.g., a stabilized FDCA-enriched fraction
  • a stabilized second fraction e.g., a stabilized TPA-enriched fraction
  • separate copolymers may be produced, such as one having furandicarboxylate moieties and preferably being substantially free of (or at least having less of) benzenedicarboxylate moieties (e.g., in the case of PEF), and another having benzenedicarboxylate (or terephthalate) moieties and preferably being substantially free of (or at least having less of) furandicarboxylate moieties (e.g., in the case of PET).
  • the stabilized composition e.g., comprising both FDCA and TPA oxidation products
  • may be used directly e.g.
  • a copolyester with one or more alcohols/polyols (e.g., ethylene glycol), such as a copolymer having both furandicarboxylate moieties and benzenedicarboxylate moieties.
  • alcohols/polyols e.g., ethylene glycol
  • these monomers may be separated as formed from the oxidation, or they may be manipulated to facilitate their separation, for example, by forming convenient derivatives of the monomers (e.g., conveniently the same (ester) derivatives as contemplated for being polymerized) which are more easily or more economically separated by reason of their having lower boiling points and/or a greater relative volatility difference, compared to their underivatized form.
  • convenient derivatives of the monomers e.g., conveniently the same (ester) derivatives as contemplated for being polymerized
  • the furanoate ester and terephthalate esters should be readily separable by distillation.
  • a resulting copolymer may be produced having, for example, both FDCA-related moieties and TPA- related moieties.
  • downstream polymerization concerns the formation of one or more homopolyesters or copolyesters from one or more of the monomers or derivatives thereof, either separately or in one or more combinations with each other and optionally other comonomers or oligomers
  • FDCA-related related moieties may be furandicarboxylate moieties and such TPA-related moieties may be terephthalate moieties (or benzene dicarboxylate moieties), obtained from polycondensation, following reaction of FDCA and/or TPA, or otherwise ester derivatives of FDCA and/or TPA, with a co-monomer having at least two hydroxyl groups (e.g., a diol).
  • a downstream polymer forming step may include reacting, as a co-monomer, a hydroxyl (alcohol) derivative of one or both of FDCA and TPA (e.g., a diol derivative of one or both of FDCA and TPA), separately or in combination, with a polyacid or its ester derivative thereof to produce a polyester having one or both of FDCA- related moieties and TPA-related moieties.
  • a hydroxyl (alcohol) derivative of one or both of FDCA and TPA e.g., a diol derivative of one or both of FDCA and TPA
  • downstream polymerization concerns the formation of one or more polyamides or copolyamides from one or more of the monomers or derivatives thereof, either separately or in one or more combinations with each other and optionally other comonomers or oligomers
  • one or both of FDCA and TPA may be reacted with a co-monomer having at least two amino groups (e.g., a diamine), to produce a polyamide having one or both of FDCA-related moieties and TPA- related moieties.
  • a downstream polymer forming step may include reacting, as a co-monomer, a hydroxyl (alcohol) derivative of one or both of FDCA and TPA (e.g., a diol derivative of one or both of FDCA and TPA), separately or in combination, with a polyisocyanate to produce a polyurethane having one or both of FDCA-related moieties and TPA-related moieties.
  • a hydroxyl (alcohol) derivative of one or both of FDCA and TPA e.g., a diol derivative of one or both of FDCA and TPA
  • a downstream polymer forming step may include reacting, as a co-monomer, an amino derivative of one or both of FDCA and TPA (e.g., a diamino derivative of one or both of FDCA and TPA), separately or in combination, with a polyacid to produce a polyamide having one or both of FDCA-related moieties and TPA-related moieties.
  • an amino derivative of one or both of FDCA and TPA e.g., a diamino derivative of one or both of FDCA and TPA
  • a downstream polymer forming step may include reacting an acyl derivative of one or both of FDCA and TPA (e.g., a diacyl chloride derivative of one or both of FDCA and TPA), separately or in combination, with a co-monomer having at least two amino groups (e.g., a diamine), to produce a polyamide having one or both of FDCA- related moieties and TPA-related moieties.
  • an acyl derivative of one or both of FDCA and TPA e.g., a diacyl chloride derivative of one or both of FDCA and TPA
  • a co-monomer having at least two amino groups e.g., a diamine
  • a downstream polymer forming step may include reacting an isocyanate derivative of one or both of FDCA and TPA (e.g., a diisocyanate derivative of one or both of FDCA and TPA), separately or in combination, with a co-monomer having at least two hydroxyl groups (e.g., a diol), to produce a polyurethane having one or both of FDCA- related moieties and TPA -related moieties.
  • an isocyanate derivative of one or both of FDCA and TPA e.g., a diisocyanate derivative of one or both of FDCA and TPA
  • a co-monomer having at least two hydroxyl groups e.g., a diol
  • inventions are directed to methods for modifying a TPA production plant comprising an oxidation reactor adapted to receive para- xylene and oxygen (or an oxygen- containing gas) as feeds, as well as a downstream terephthalic acid crystallization and recovery section configured to separate solvent from TPA and recycle it to the oxidation reactor.
  • the methods comprise retrofitting the terephthalic acid production plant with a connection from an existing inlet of the oxidation reactor, or from an added inlet of the oxidation reactor, to an upstream carbohydrate dehydration reactor.
  • the present invention relates to the discovery that the para-xylene can be suitably employed as a co-solvent, e.g., for furanic precursors of FDCA, in an upstream carbohydrate dehydration reactor preliminary to a co-oxidation of both a dehydration product of one or more hexoses and para- xylene to generate a mixed monomer composition where, for example, in the retrofit scenario just given there is a connection made from an inlet of an existing oxidation reactor for converting para- xylene to TPA to such an upstream carbohydrate dehydration reactor.
  • a co-solvent e.g., for furanic precursors of FDCA
  • At least a portion of the para- xylene to be oxidized for providing a corresponding portion of the mixed monomer composition can be introduced via the product mixture from an upstream carbohydrate dehydration reactor alongside one or more FDCA-forming furanics generated therein.
  • the dehydration utilizes hydrobromic acid in addition to acetic acid and is integrated with a subsequent Mid-Century type oxidation step so that the dehydration product is fed directly into the subsequent oxidation step as described in US 10,538,499
  • at least a portion of the para-xylene can in fact displace a portion of the substantial quantities of acetic acid that in US 10,538,499 are contemplated as optimally being recovered and recycled following the oxidation step, so that capital and operating expenses associated with this recycle can be reduced.
  • the amount of heat energy generated in the co-oxidation step relative to the amount of acetic acid needing to be recycled in an integrated process conducted otherwise in keeping with US 10,538,499 is significantly increased, enabling the energy costs associated with the recycle acetic acid stream to be at least partially offset.
  • an amount of para-xylene is fed to the oxidation step from a preceding dehydration step that can be well in excess of that amount that would be indicated for providing a stabilizing effect or benefit as previously described in consideration of what humins are present in the materials to be supplied to the oxidation step - for example, in certain embodiments, up to 20 weight percent of that portion of the feed for generating a mixed monomer composition in a subsequent oxidation step (especially utilizing a Mid-Century type oxidation but optionally using another oxidation catalyst, as exemplified below) that is obtained from a carbohydrate dehydration step may be para-xylene.
  • FIG. 1 illustrates a multi-step process for making a copolymer by forming a mixed monomer composition and using this in a polymer forming step.
  • FIG. 2 illustrates a multi-step process according to which the mixed monomer composition is separated into fractions, prior to using one or both fractions in a polymer forming step.
  • FIG. 3 illustrates the use of a carbohydrate dehydration reactor for modifying a terephthalic acid production plant.
  • FIG. 4 provides a Table of experimental results associated with the Examples below.
  • FIG. 5 provides a second Table of experimental results associated with the Examples below.
  • FIGS. 1-3 represent the same or similar features.
  • FIGS. 1-3 should be understood to present simplified overviews of processes and their associated equipment, in order to demonstrate certain principles involved.
  • the depicted elements are not necessarily drawn to scale; nor do the illustrated processes and equipment associated therewith preclude the addition of any upstream, intermediate, or downstream steps, such as separating, combining, and/or reacting steps.
  • an intermediate recycling step could involve both separating and combining.
  • other processes may have alternative configurations and/or components that are governed by specific operating objectives, but which alternatives are nonetheless within the scope of the invention as defined by the appended claims.
  • Certain aspects of the invention relate to processes in which a dehydration product, such as the product of the dehydration of a hexose carbohydrate (e.g., fructose), is subjected to oxidation in the presence of a “co-feed,” which may be considered a “stabilizing co-feed” to the extent that it provides or is available to provide oxidation reaction stabilizing benefits as described herein.
  • a co-feed itself may become oxidized to yield a useful product, such as a second monomer that is different from a monomer obtained from oxidation of the dehydration product.
  • co-feed or “stabilizing co-feed” can also be characterized in such cases as a “second monomer-forming co-feed.”
  • co feed should not be interpreted to impose any limitation on the amount of its addition or presence relative to that of the dehydration product or any portion thereof, such as the “on path” FDCA-forming furanics portion that is oxidizable to a desired monomer, such as FDCA.
  • particular embodiments described herein are directed to the addition of the co feed in sub-stoichiometric amounts, or at a molar ratio of less than 1, relative to the moles of FDCA-forming furanics, whereas other embodiments are directed to its addition in excess stoichiometric amounts, or at a molar ratio of greater than 1.
  • the latter case may arise, for example, in the case of retrofitting an existing facility (plant) used for the oxidation of p-xylene to make TPA, in order to accommodate a relatively minor addition of a dehydration product as a source of a bio-derived monomer as might be desired, for example, in the early commercialization of FDCA.
  • wt-% and wt-ppm are used to designated percentage by weight and parts per million by weight, respectively.
  • mol-% is used to designate a molar percentage.
  • the phrase “being (or is) substantially free of,” can mean, in various embodiments, “having (or has) less than 5 wt-% of,” “having (or has) less than 3 wt-% of,” or “having (or has) less than 1 wt-% of.”
  • byproducts such a humin byproducts and color- forming byproducts, these may alternatively be referred to as “contaminants” or “impurities”.
  • FDCA 2,5-furandicarboxylic acid
  • TP A terephthalic acid
  • Certain processes expressly include steps of “esterifying” to form ester derivatives of FDCA and TPA, whereby one or preferably both of the carboxylic acid groups of these dicarboxylic acids are instead ester groups, such as alkyl ester groups (in the case of a mono- or dialkyl ester derivative) or aryl ester groups (in the case of a mono- or diaryl ester derivative), with methyl ester groups, ethyl ester groups, or phenyl ester groups being specific examples.
  • the preferred ester derivative of FDCA is 2,5-furandicarboxylic acid, dimethyl ester (FDME) and the corresponding preferred ester derivative of TPA is dimethyl terephthalate (DMT), which can be formed by reaction of FDCA and TPA, respectively, with sufficient quantities of methanol.
  • DMT dimethyl terephthalate
  • one or both of the two carboxy-substituted furan ring members of FDCA or one of both of the two carboxy-substituted benzene ring members of TPA may instead be substituted with carboxylic acid groups other than carboxy and/or with these other groups, to provide, for example, the corresponding diol, dialkanol (e.g., dimethanol), diamino, diacyl (e.g., diacyl chloride), diester, diisocyanate, ether-acid, ether-ester, ester-acid, ester-aldehyde, ether-aldehyde, ether-acetal, ester-acetal, acetal-acid, hydroxyl-acid, hydroxyalkyl-acid, hydroxyl-ester, hydroxyalkyl-ester, hydroxyl-acetal, hydroxyalkyl-acetal, hydroxyalkyl-acetal, hydroxyalkyl-acetal, hydroxyalkyl-
  • the formation of these various derivatives from the exemplary monomers FDCA and TPA may be desirable in relation to the mixed monomer composition for facilitating a separation of the mixed monomer composition into a fraction enriched in FDCA and preferably substantially completely depleted in TPA on the one hand, and a fraction enriched in TPA and preferably substantially completely depleted in FDCA on the other, and in general, for addressing the tendency of any aldehyde-containing species from the oxidation to undergo aldol condensation and produce color over time in the mixed monomer composition or in the enriched monomer fractions having these aldehyde- containing species.
  • ester derivatives are particularly appropriate for accomplishing these objectives in the context of producing the homopolyester and copolyester polymers in which TPA and FDCA are expected to be most commonly commercially employed, but those of skill in the polymerization art will certainly be well able to conceive of other derivatives of FDCA and TPA that will be able to be employed in a subsequent polymer forming step and of the relative advantages and disadvantages of these various possible derivatives in the context of making a desired polymer product or combination of polymer products.
  • ester derivatives like their parent carboxylic acid (e.g., dicarboxylic acid) compounds, these may be used as monomers in polymer forming steps as described herein. Therefore, any such ester derivative may be equivalently referred to as an “ester derivative monomer”; consistent with the preceding paragraph, however, the fact that hereafter we will address and describe predominantly the “ester” derivatives and the “esterification” of the FDCA and TPA diacids should not be taken as implying that other derivatives as just described may not also be used as monomers in subsequent polymer forming steps, but rather as reflecting only the expectation that the co-produced FDCA and TPA will most commonly be destined for application in the manufacture of polyester products.
  • carboxylic acid e.g., dicarboxylic acid
  • ester derivatives or “esterification” will be understood as including any other form of derivative or derivatization of FDCA and/or TPA, unless those skilled in the art would understand in context that only the ester derivatives or esterification may reasonably be contemplated.
  • the processes may comprise contacting an oxidation feed, in the presence of oxygen (e.g. , in an oxygen-containing feed such as air), with an oxidation catalyst to provide the mixed monomer composition.
  • the oxidation feed may comprise (i) a dehydration product of one or more carbohydrates (e.g., fructose) having a 6-carbon sugar unit, and (ii) para- xylene.
  • Component (i) of the oxidation feed may thus comprise FDCA-forming furanics, and representative processes may comprise feeding both components (i) and (ii) to an oxidation reactor containing an oxidation catalyst (e.g., a homogeneous or heterogeneous catalyst) and reactant oxygen.
  • an oxidation catalyst e.g., a homogeneous or heterogeneous catalyst
  • a carbohydrate having a six-carbon sugar unit means a six-carbon sugar, an oligomer of a six-carbon sugar, or a polymer of a six-carbon sugar.
  • Such carbohydrates include starch, amylose, galactose, cellulose, hemicellulose, inulin, fructan, glucose, fructose, sucrose, maltose, cellobiose, lactose, and sugar oligomers.
  • These carbohydrates may also be referred to as hexose carbohydrates and may be obtained from one or a combination of products, byproducts, or intermediate products of a wet or dry grain milling process, with such products including one or more of fructose syrup, crystalline fructose, high fructose com syrup, crude fructose, purified fructose, or molasses.
  • a preferred carbohydrate is fructose, which may be provided to the dehydration step in pure or purified form (e.g., at greater than 90% or 95% purity).
  • FDCA-forming furanics refer to furan ring-containing monomeric and dimeric molecules which form FDCA through catalytic oxidation as described herein.
  • FDCA-forming furanics, along with unwanted byproducts may be obtained as the dehydration product, from dehydrating one or more carbohydrates having a six-carbon sugar unit at elevated temperatures and in the presence of an acid catalyst, which may be homogeneous or heterogeneous in nature.
  • FDCA-forming furanics include 5-(hydroxymethyl)furfural (HMF), and, in the case of their formation in the presence of a lower carboxylic acid (i.e.
  • a Ci to Ce aliphatic carboxylic acid such as acetic acid
  • a Ci to Ce aliphatic alcohol e.g. , methanol
  • Other FDCA-forming furanics can include derivatives of HMF such as 2,5-diformylfuran, and 5-formyl-2-furancarboxylic acid.
  • FDCA-forming furanics further include the HMF dimer 5,5'-[oxybis(methylene)]di(2-furaldehyde), as well as HMF oligomers.
  • HMF dimer 5,5'-[oxybis(methylene)]di(2-furaldehyde) examples include, but are not limited to, furfural, 2-(hydroxyacetyl)furan, and 2-(acetoxyacetyl)furan.
  • the dehydration product may comprise, such that the FDCA-forming furanics may include, one or more of HMF and/or an ester or ether derivative thereof.
  • the FDCA-forming furanics may include HMF, 5-(acetoxymethyl)furfural, and HMF dimer.
  • the dehydration utilizes hydrobromic acid in addition to acetic acid and is integrated with a subsequent Mid-Century type oxidation step so that the dehydration product is fed directly into the subsequent oxidation step consistent with US 10,538,499, except that a stabilizing co-feed is also supplied to the subsequent oxidation step.
  • ester derivatives of HMF are to be understood to be compounds which would or do result from the esterification of the hydroxyl group of HMF with a carboxylic acid via condensation reaction, e.g. the condensation of acetic acid and the hydroxyl group of HMF to furnish 5- (acetoxymethyl)furfural.
  • ether derivatives of HMF are to be understood to be compounds which would or do result from the etherification of the hydroxyl group of HMF, e.g. the etherification of the hydroxyl group of HMF under methylating conditions to furnish 5-(methoxymethyl)furfural.
  • an oxidation feed comprises a dehydration product, such as a product including FDCA-forming furanics
  • at least two processing steps may be performed, namely the steps of (i) dehydrating the carbohydrate having a six-carbon sugar unit to provide a dehydration product comprising FDCA-forming furanics, and (ii) oxidizing the dehydration product, in an oxidation feed further comprising para-xylene, to provide FDCA, together with TPA.
  • steps may be integrated as described above, providing advantages that may include the use of the same acetic acid (or acetic acid and water) solvent in both steps.
  • the use of a common solvent in addition to the suitability of hydrobromic acid for use as a further acid catalyst for the dehydration step, provides the added advantage that acetic acid and optionally at least a portion of the bromine source for the Mid-Century oxidation step (in the form of hydrobromic acid, typically), can be recycled (and preferably substantially completely recycled) from the oxidizing step back to the dehydrating step.
  • the integrated process is amenable to being fabricated by retrofitting existing equipment used in such oxidations, for example, in the oxidation of p-xylene to make TPA.
  • the oxidizing step may be performed by adding a co-feed such as para- xylene that imparts or is available to impart a reaction stabilizing effect as described above, the latter scenario being contemplated where a dehydration product is not fed directly and without any intervening further processing to the oxidizing step, such intervening processing, for example, being in the way of refining or purification to remove humins from the dehydration product as a whole or in the form of some kind of pretreatment of humins in the dehydration product to mitigate or at least partly mitigate the detrimental effects of at least those same species of humins therein addressed by the reaction stabilizing effect of the co-feed.
  • a co-feed such as para- xylene that imparts or is available to impart a reaction stabilizing effect as described above
  • reaction stabilizing effect can be realized with a relatively minor amount of the co-feed (if appropriate and desired, given a manufacturer’s desired product mix in a mixed monomer composition comprising both FDCA and a second monomer such as TP A), which providentially also serves as a source of a second monomer.
  • the reaction stabilizing effect may be realized with adding the co-feed (e.g., batchwise or continuously to an oxidation reactor) in an amount representing less than 50 mol- %, based on the number of moles (e.g., based on the total number of moles of HMF, 5- (acetoxymethyl)furfural, and HMF dimer) of FDCA-forming furanics being oxidized.
  • the co-feed may be added in a sub- stoichiometric (sub-molar) amount representing less than 45 mol-% (e.g., from 5 mol-% to 45 mol-%) of the FDCA-forming furanics.
  • the co-feed e.g., para- xylene
  • the co-feed may be added in a sub- stoichiometric amount representing less than 80 mol-% (e.g., from 10 mol-% to 80 mol-% or from 30 mol-% to 60 mol-%), of the FDCA-forming furanics.
  • a greater amount such as a stoichiometric equivalent (molar equivalent) amount, or excess stoichiometric (excess molar) amount, of the co-feed may be desirably added, for example, to produce a second monomer in a greater proportion to the first monomer as well as provide the reaction stabilizing effect for the production of the first monomer, and the process of the present invention possesses the operational flexibility to accommodate this scenario as well.
  • the co-feed may be added in an amount representing greater than 85 mol- % (e.g., from 85 mol-% to 200 mol-%), greater than 90 mol-% (e.g., from 90 mol-% to 150 mol-%), or greater than 100 mol-% (e.g., from 100 mol-% to 125 mol-%), of the FDCA- forming furanics.
  • this may be an amount representing greater than 125 mol-% (e.g., from 125 mol-% to 1000 mol-%), greater than 150 mol-% (e.g., from 150 mol-% to 500 mol-%), or greater than 200 mol-% (e.g., from 200 mol-% to 400 mol-% or from 300 mol-% to 400 mol-%) of the FDCA-forming furanics.
  • an oxidation feed that comprises (i) a dehydration product of one or more carbohydrates (e.g., having a six-carbon sugar unit), and (ii) a second monomer- forming co-feed (e.g., para- xylene), the latter may represent at least 1 wt-% of the combined amount of (i) and (ii).
  • the co-feed may be present in an amount representing from 1 wt-% to 75 wt-%, from 2 wt-% to 45 wt-%, or from 5 wt-% to 35 wt-%, of the combined amount of (i) and (ii).
  • these feeds (i) and (ii) may be provided as separate streams (e.g., input at separate locations) to the same oxidation reactor.
  • the separate streams may enable a more desirable temperature profile within the oxidation reactor, or otherwise provide improved control over this temperature profile, such as by positioning or manipulating the exothermic heat release.
  • the feeds (i) and (ii) may be provided as a combined feed stream to an oxidation reactor, such as in the case of combining a stream of para- xylene with the effluent of a dehydration reactor comprising the FDCA-forming furanics.
  • portions of the feeds (i) and (ii) may be combined upstream of the oxidation reactor and/or added as separate streams to the oxidation reactor, depending on objectives relating to process efficiency and process control.
  • the co-feeding may be further combined, in an integrated or non-integrated manner, with a further step, prior to the co-feeding, of dehydrating one or more carbohydrates to obtain the FDCA-forming furanics.
  • This dehydrating may be performed with the one or more carbohydrates (e.g. , selected from hexose sugars) being in a solution comprising, as a solvent, a lower carboxylic acid (e.g., acetic acid) or a lower alcohol (e.g., methanol or ethanol).
  • a lower carboxylic acid e.g., acetic acid
  • a lower alcohol e.g., methanol or ethanol
  • particular embodiments of the invention are directed to processing options, as well as overall processing flexibility, arising from the use of a second monomer forming co-feed.
  • Specific options relate to processing steps downstream of dehydrating and oxidizing steps for making the comprising two monomers, or mixed monomer composition.
  • the dehydrating and oxidizing steps are further described below, as well as additional, and optional, steps of removing or modifying problematic humin species, color stabilizing, esterifying (or derivatizing in some other fashion, more generally), separating, and polymer forming, which may be performed in various orders and according to various configurations described, with further reference to specific orders and configurations illustrated in the figures.
  • Representative processes comprise, prior to an oxidizing step, a dehydrating step for making FDCA-forming furanics as described above, all or a portion of which are used in (e.g., as a component of an oxidation feed for, or as a stream for co-feeding to), this oxidizing step.
  • the dehydrating step may be performed batchwise, whereby the FDCA-forming furanics are recovered and intermittently transferred to the oxidizing step, but preferably the dehydrating step is performed continuously with continuous transfer.
  • an upstream step of the process may therefore comprise dehydrating a dehydration feed comprising one or more carbohydrates having a six-carbon sugar unit, as described above.
  • This dehydration feed (e.g., an aqueous fructose solution) may have a dry solids concentration from 5 wt-% to 50 wt-%, such as from 10 wt-% to 30 wt-% and/or may be prepared from a purified source of the six- carbon sugar such as fructose having a purity of at least 90 wt-% (e.g., 97 wt-% fructose).
  • the dehydrating may occur in the presence of a bromine source and a solvent for the FDCA- forming furanics, and may be performed at an elevated temperature and for a time sufficient to generate the oxidation feed comprising FDCA-forming furanics, such as HMF and/or its derivatives.
  • the derivative(s) may include an ester derivative, an ether derivative, and/or HMF dimer.
  • the oxidation feed comprising some or all of the product formed in the dehydrating step (dehydration product) as a component, will generally also comprise at least a portion of the solvent. That is, all or a portion of the solvent, such as a mixture of acetic acid and water, that is used in the dehydrating step, may be passed to the oxidizing step, in addition to all or a portion of any water generated in this step.
  • the solvent may otherwise comprise an alcohol such as methanol, ethanol, or a higher alcohol, or possibly a cyclic or heterocyclic hydrocarbon compound (e.g. , dioxane).
  • Solvent is preferably separated following the oxidizing step to provide, in addition to a mixed monomer composition or co product as described herein, a solvent recycle stream back to the dehydrating step.
  • the solvent recycle stream may contain FDCA-forming furanics, such that the total amount of FDCA- forming furanics in the dehydration product may include a portion that has been newly generated in a pass through the dehydrating step (i.e. , based on a “per-pass conversion”) and a portion that has been recycled back from the downstream oxidizing step.
  • the solvent used in the dehydrating step may be, or may comprise, all or a portion of the co-feed such as para- xylene.
  • all or a portion of the co-feed added to the downstream oxidizing step may be present in the dehydration product, together with the FDCA-forming furanics.
  • a second portion may be added directly to the oxidizing step (e.g., oxidation reactor), whereas a fresh, makeup portion of the co-feed may be added directly to the dehydrating step (e.g. , dehydration reactor) or otherwise to a solvent recycle that is separated from an effluent of the oxidizing step (e.g., oxidation reactor) and fed back to the dehydrating step (e.g. , dehydration reactor).
  • the portion of the co-feed present in the dehydration product may represent a combined amount of the fresh, makeup portion and an amount present in the solvent recycle (e.g. , at steady-state operation).
  • the overall material requirement and expenses associated with the use of a conventional solvent or component thereof (e.g., acetic acid) that does not undergo oxidation to form a second monomer, or oxidation at all, is advantageously reduced or even eliminated altogether.
  • co-feed added to the dehydrating step serves as an effective solvent for the FDCA-forming furanics and also becomes oxidized to a second monomer of a mixed monomer composition obtained in an effluent of the oxidizing step
  • solvent recycle operating duties and associated expenses may be reduced or even eliminated altogether.
  • productivity of the oxidizing step may be significantly increased, for example based on the molar production rate of one or more monomers (e.g., one of both of FDCA and TP A) per unit volume of the oxidation reactor.
  • the bromine source used in the dehydrating step can be any compound that provides bromide ions or radicals in the reaction mixture.
  • Representative bromine sources include hydrogen bromide, hydrobromic acid, sodium bromide, potassium bromide, molecular bromine, benzyl bromide, and tetrabromoethane.
  • this compound in the presence of the dehydration feed and solvent, may act as an acid catalyst in the dehydrating step, upon dissociation to form hydrobromic acid.
  • bromine sources such as 1-alkylpyridinium bromides and 1,3- dialkylimidazolium bromides may be useful as promoters in the presence of a solvent comprising acetic acid and water.
  • the step of dehydrating therefore provides a dehydration product, some or all of which may be used a component of the subsequent oxidizing step, together the stabilizing co-feed as described herein, used to form a second monomer.
  • a dehydration product some or all of which may be used a component of the subsequent oxidizing step, together the stabilizing co-feed as described herein, used to form a second monomer.
  • Particular methods for dehydrating are described, for example, in US 10,538,499, wherein both of hydrobromic acid and acetic acid are present for the dehydration of especially fructose and then supplied for use in a subsequent Mid-Century oxidation step.
  • the step of dehydrating may result in the formation, in the dehydration product comprising FDCA-forming furanics, of humins as byproducts.
  • Humins refer to highly colored, generally brown to black, amorphous or non-crystalline polymers resulting from the dehydration of sugars.
  • concentration of humins in the dehydration product will depend at least partly on conditions, and particularly reaction severity, used in the dehydrating step, such that this concentration may correlate with the per-pass conversion.
  • representative processes may further comprise a step of separating at least a portion of the humins from the dehydration product, prior to the oxidizing step (e.g., to provide an oxidation feed having a reduced concentration of humins relative to the dehydration product).
  • the reaction stabilizing effect of using para- xylene or other second monomer-forming co-feed with the dehydration product may lessen, or even eliminate, the need for humin removal, upstream of the oxidizing step.
  • the dehydration product is not treated to remove humins, prior to the oxidizing step.
  • the humin content of FDCA-forming furanics obtained in the dehydrating step is not reduced by filtration or other suitable means of separating out at least some of the humins from the dehydration product, before co-feeding the dehydration product with para-xylene to an oxidation reactor.
  • a purified portion of the dehydration product as described herein which comprises purified HMF and/or other FDCA-forming furanics and which is obtained following the removal (e.g., by ultrafiltration) of a contaminant portion of the dehydration product that is enriched in humins, can nonetheless benefit from the addition of a co-feed (e.g. , para- xylene) in terms of ameliorating reaction instability occurring under oxidation conditions and further in enabling retrofit scenarios to take advantage of underutilized para-xylene oxidation capacity.
  • a co-feed e.g. , para- xylene
  • representative processes comprise removing at least a portion of humins in the dehydration product, prior to (upstream of) the oxidizing step (e.g., to provide the oxidation feed).
  • the dehydration product may be subjected to filtration, such as using an ultrafiltration (UF) membrane, taking advantage of the general insolubility of humins in water.
  • UF ultrafiltration
  • Other methods for removing humins from the dehydration product, or from other intermediate products in the overall synthesis of bio-based polymer include distillation and sublimation. Particular methods for humin removal are described, for example, in US 10,457,657.
  • Representative methods comprise contacting an oxidation feed, in the presence of oxygen, with an oxidation catalyst to provide a mixed monomer composition or co-product as described herein, which may comprise FDCA and a second monomer formed from the use of a co-feed such as para- xylene as a second component of the oxidation feed.
  • a mixed monomer composition or co-product as described herein which may comprise FDCA and a second monomer formed from the use of a co-feed such as para- xylene as a second component of the oxidation feed.
  • a first component of the oxidation feed all or a portion of the dehydration product (e.g. , comprising FDCA-forming furanics) may be used, such as a portion obtained following the removal of humins as described above.
  • the oxidation feed may further comprise all or a portion of the solvent used to prepare the dehydration feed and/or at least one bromine-containing species.
  • the oxygen may be obtained using, as a source, air, purified oxygen, or other oxygen- containing feed.
  • the oxidizing step may be performed batchwise, but is preferably performed continuously, with at least the dehydration product (or a portion thereof), co-feed, and oxygen- containing feed, and optionally catalyst, being fed continuously to an oxidation reactor, and the mixed monomer composition being continuously withdrawn from this reactor.
  • Particular methods may comprise contacting the oxidation feed, as described above, with a metal-containing catalyst and the oxygen-containing feed at an elevated temperature for a time sufficient to produce, as an oxidation product, a mixed monomer composition comprising FDCA and/or its derivatives, a second monomer formed from oxidation of the co feed (e.g., TPA formed from oxidation of para-xylene), solvent, and residual catalyst.
  • a mixed monomer composition comprising FDCA and/or its derivatives
  • a second monomer formed from oxidation of the co feed e.g., TPA formed from oxidation of para-xylene
  • solvent e.g., oxidation of para-xylene
  • bromine-containing species include inorganic bromides such as HBr; metal bromides such as lithium bromide, sodium bromide, potassium bromide, magnesium bromide, calcium bromide, cobalt bromide, and manganese bromide; and organic bromides such as 5-(bromomethyl) furfural and derivatives thereof, and brominated furanic oligomers.
  • a bromine source may be introduced to the oxidizing step (e.g., fed to the oxidation reactor), if necessary to supplement the bromine content that is provided by the bromine-containing species in the oxidation feed, which originate in the dehydrating step.
  • metal-containing catalysts in particular can be effective for converting HMF and/or other FDCA-forming furanics (e.g. , HMF esters and/or HMF ethers) in the oxidation feed (depending on the solvent used in the dehydrating step) to FDCA and/or its derivatives.
  • Representative metal-containing catalysts may comprise one or more transition metals, such as either or both of Co and Mn, optionally in combination with Zr or Ce.
  • the metal-containing catalyst may react with the bromine present in the bromine-containing species, as described above, to form metal bromides in situ.
  • the metal catalyst may be present in a reaction mixture that is contained in the oxidation reactor, such that the concentrations of the one or more transition metals are independently in the range from 5 wt-ppm to 10,000 wt-ppm, such as from 10 wt-ppm to 8,000 wt-ppm or from 50 wt-ppm to 5,000 wt-ppm.
  • Co may be present in the reaction mixture in a concentration from 10 wt-ppm to 10,000 wt-ppm, from 10 wt-ppm to 8,000 wt-ppm, from 59 wt-ppm to 5,900 wt-ppm, or from 2,000 to 4,000 wt-ppm.
  • Mn may be present in the reaction mixture in a concentration from 5 wt-ppm to 10,000 wt-ppm, from 5 wt-ppm to 8,000 wt-ppm, from 55 wt-ppm to 5,500 wt-ppm, or from 200 to 1 ,000 wt-ppm.
  • Bromine, from the bromine-containing species and/or bromine source may be present in the reaction mixture from 0.1 wt-ppm to 20,000 wt-ppm, from 200 wt-ppm to 20,000 wt-ppm, from 10 wt-ppm to 10,000 wt-ppm, or from 1,000 wt-ppm to 2,000 wt-ppm.
  • Oxidizing conditions, or conditions maintained in the oxidizing reactor may include a temperature from 120°C to 250°C, such as from 170°C to 190°C, and an oxygen partial pressure from 0.02 bar to 100 bar, from 0.02 bar to 21 bar, from 0.2 bar to 100 bar, or from 0.2 bar to 21 bar.
  • the total absolute pressure in the oxidizing reactor may be from 1 bar to 200 bar, such as from 5 bar to 100 bar or from 10 bar to 20 bar.
  • Molar yields of monomers from the oxidizing step may be at least 60%, at least 70%, at least 80%, at least 90%, or at least 95%.
  • the resulting monomers such as FDCA and/or TPA may be separated from the oxidation reaction mixture, including the solvent, for further purification. At least a portion of the solvent, from which these monomers are separated, may then be recycled back to the dehydration reactor, together with at least a portion of unconverted FDCA-forming furanics.
  • FDCA and TPA are largely insoluble in acetic acid or in mixtures of acetic acid and water under mild conditions
  • separation of FDCA and/or TPA in such embodiments may be easily accomplished by filtration and/or centrifugation following their precipitation from the oxidation reaction mixture.
  • Particular methods for oxidizing are described, for example, in US 10,538,499.
  • the oxidizing step that is used to form a mixed monomer composition comprising two monomers may also generate color-forming byproducts to some extent, which contribute to an initial presence of color (preventing a desired, colorless appearance) and/or to forming color bodies over time, such as through aldol condensation reactions under acidic conditions that lead to increasing molecular weight.
  • Particular color-forming byproducts are aldehyde derivatives of these monomers.
  • this composition may further comprise, in independent amounts, generally from 0.1 wt-% to 15 wt-%, typically from 0.3 wt-% to 10 wt-%, and often from 1 wt-% to 3 wt-%, of (i) 5-formyl-2-furancarboxylic acid (FFCA) resulting from incomplete oxidation of FDCA and/or (ii) 4-carboxybenzaldehyde (4- CBA) resulting from incomplete oxidation of TPA.
  • FFCA 5-formyl-2-furancarboxylic acid
  • 4-carboxybenzaldehyde (4- CBA
  • the mixed monomer composition from the oxidation step and/or separated fractions of the mixed monomer composition that are enriched in either a first monomer or a second monomer may be subjected to a further derivatization step calculated to prevent their participation in aldol condensation reactions leading to the development of unwanted color, for example, an esterification step.
  • this composition may further comprise, in independent amounts, generally from 0.1 wt- % to 15 wt-%, typically from 0.3 wt-% to 10 wt-%, and often from 1 wt-% to 3 wt-%, of (i) 5-formyl-2-furancarboxylic acid methyl ester (FFME) resulting from the esterification of FFCA and (ii) 4-carboxybenzaldehyde methyl ester (4-CME) resulting from the esterification of 4-CBA.
  • FFME 5-formyl-2-furancarboxylic acid methyl ester
  • 4-CME 4-carboxybenzaldehyde methyl ester
  • representative processes include forming products resulting from steps from the dehydrating step to the polymer forming step, and these products may include one or more of: a mixed monomer composition; an esterified mixed monomer composition; a separated fraction that is enriched in a given monomer; or an esterified, separated fraction that is enriched in an ester derivative of such monomer.
  • any of such products may be subjected to a further color stabilizing step, in contemplation, for example, of the presence in even an esterified mixed monomer composition or in the esterified, separated monomer-enriched fractions of FFME and 4-CME or the presence in the underivatized mixed monomer composition or separated monomer-enriched fractions of aldehydes such as FFCA and 4-CBA, according to which the product is contacted with a color stabilizing medium, for example to reduce the content of one or more color- forming aldehydes and/or otherwise reduce the color of such product or render it less susceptible to color formation.
  • a further color stabilizing step for example, of the presence in even an esterified mixed monomer composition or in the esterified, separated monomer-enriched fractions of FFME and 4-CME or the presence in the underivatized mixed monomer composition or separated monomer-enriched fractions of aldehydes such as FFCA and 4-CBA, according to which the product is contacted with a color stabilizing medium, for example
  • a color stabilizing step comprises contacting (i) a mixed monomer composition comprising two monomers, or (ii) a separated fraction thereof that may be enriched in a given monomer (relative to the mixed monomer composition from the oxidation step), (iii) an esterified mixed monomer composition comprising two ester derivatives of two monomers, or (iv) a separated fraction thereof that may be enriched in a given ester derivative of a monomer (relative to the esterified mixed monomer composition), with hydrogen, as the color stabilizing medium, to selectively hydrogenate a color-forming aldehyde byproduct, including any of the particular aldehyde byproducts described above.
  • Color-forming aldehyde byproducts may be selectively hydrogenated under suitable hydrogenation conditions, whereby their aldehyde groups are converted to hydroxy alkyl groups to produce the corresponding hydroxy alkyl derivatives of these byproducts.
  • a byproduct that is an aldehyde derivative of FDCA or of an ester derivative of FDCA in which the aldehyde group is a formyl group
  • such byproduct may be selectively hydrogenated to its hydroxymethyl derivative.
  • FFCA an aldehyde derivative of FDCA
  • this byproduct may be selectively hydrogenated to its hydroxymethyl derivative, 5- hydroxymethyl-2-furancarboxylic acid (HMFCA).
  • this byproduct may be selectively hydrogenated to its hydroxymethyl derivative, 5-hydroxymethyl-2-furancarboxylic acid methyl ester (HMFME).
  • HMFME 5-hydroxymethyl-2-furancarboxylic acid methyl ester
  • 4-CBA an aldehyde derivative of TP A
  • this byproduct may be selectively hydrogenated to its hydroxymethyl derivative, 4-hydroxymethyl-benzoic acid (4-HMBA).
  • 4-CME an aldehyde derivative of DMT, which is an ester derivative of TP A
  • this byproduct may be selectively hydrogenated to its hydroxymethyl derivative, methyl (4-hydroxymethyl)benzoate (4-HMMB).
  • the contacting may be carried out in the presence of a hydrogenation catalyst, typically in solid form and comprising at least one noble metal, to produce a corresponding, stabilized composition (stabilized mixed monomer composition) or separated fraction, or otherwise a stabilized, esterified composition (stabilized, esterified mixed monomer composition) or separated fraction.
  • a hydrogenation catalyst typically in solid form and comprising at least one noble metal
  • Particular hydrogenation catalysts that can selectively hydrogenate aldehyde byproducts described herein, advantageously without substantially hydrogenating the furan rings or benzene rings of the corresponding monomers or ester derivative monomers, comprise the noble metals Pt and Ru, together with the promoter metal Sn.
  • Other possible methods for the reduction of aldehyde byproducts are described in International Application PCT/US2018/041694 (published as WO 2019/014382),.
  • a color stabilizing step comprises contacting (i) a mixed monomer composition comprising two monomers, or (ii) a separated fraction thereof that may be enriched in a given monomer (relative to the mixed monomer composition), (iii) an esterified mixed monomer composition comprising two ester derivatives of two monomers, or (iv) a separated fraction thereof that may be enriched in a given ester derivative of a monomer (relative to the esterified mixed monomer composition), with a color stabilizing additive compound, as the color stabilizing medium.
  • Color stabilizing additive compounds can advantageously reduce the extent of color formation during periods (e.g., prolonged storage periods) between the synthesis of monomer(s) and its/their use in the production of bio-based polymer(s) as described herein.
  • the “contacting” with a color stabilizing additive compound may therefore result in a mixed monomer composition, separated fraction, or otherwise an esterified mixed monomer composition or separated fraction as described herein, comprising one or more color stabilizing additive compounds.
  • compositions may comprise, consist of, or consist essentially of, monomer(s) (e.g., FDCA and TPA in combination, or in separated fractions enriched in one or the other) or their ester derivative(s) (e.g., FDME and DMT in combination, or in separated fractions enriched in one or the other) and one or more color stabilizing additive compounds.
  • monomer(s) e.g., FDCA and TPA in combination, or in separated fractions enriched in one or the other
  • ester derivative(s) e.g., FDME and DMT in combination, or in separated fractions enriched in one or the other
  • color stabilizing additive compounds e.g., FDME and DMT in combination, or in separated fractions enriched in one or the other
  • a color stabilizing step may comprise, for example, melting the monomer(s) or ester derivative(s) of interest, dispersing the desired color stabilizing additive compound(s) uniformly into the melt, and optionally solidifying the resulting, stabilized composition (e.g., by active cooling or simply allowing the composition to return to ambient conditions).
  • the desired color stabilizing additive compound(s) may be introduced directly into (a) the oxidation feed for synthesis of the mixed monomer composition (b) any stream of a given mixed monomer composition, separated fraction, or otherwise an esterified mixed monomer composition or separated fraction as described herein, which is used in a polymer forming step, and/or (c) introduced into a reaction mixture of the polymer forming step, at any sub-step such as (i) esterifying or transesterifying, and (ii) polymerizing by polycondensation.
  • Representative color stabilizing additive compounds include substituted phenols, which refer to compounds having at least one phenol moiety, but possibly two or more phenol moieties, in which the benzene ring(s) of such moiety or moieties have at least one substituent, other than the hydroxyl substituent.
  • substituents are alkoxy and alkyl substituents, with methoxy and ieri-butyl substituents being preferred.
  • substituted phenols include alkoxy-substituted (e.g., methoxy-substituted) and alkyl-substituted (e.g., tert-butyl- substituted) phenols, which are namely compounds having at least one phenol moiety, but possibly two or more phenol moieties, with one or more alkoxy (e.g., methoxy) and alkyl (e.g., /7-butyl) substituents, respectively.
  • these compounds are often referred to as “hindered phenols,” in view of the steric hindrance resulting from the geometry of these substituents.
  • Substituted phenols include butylated hydroxyanisole (BHA); 2,6-dimethoxyphenol (DMP); 2,6-di-/ ⁇ ? r/-butyl-4-methoxylphenol (DTMP); pentaerythritol tetrak i s 13 - 13 , 5 -di - / ⁇ ? rt - butyl-4-hydroxyphenyl]propionate (PETC); 2-/ ⁇ ? r/-butylhydroquinone (TBHQ); ethylenebis (oxyethylene) bis-(3-(5-/ ⁇ ?
  • BHA butylated hydroxyanisole
  • DMP 2,6-dimethoxyphenol
  • DTMP 2,6-di-/ ⁇ ? r/-butyl-4-methoxylphenol
  • PETC pentaerythritol tetrak i s 13 - 13 , 5 -di - / ⁇ ? r
  • BHA, DMP, and DTMP are methoxy-substituted phenols
  • r/-butyl-4- hydroxyphenyl)-propionate are /7-butyl -substituted phenols.
  • Other color stabilizing additive compounds include phenyl-substituted amines (e.g., 4,4'-bis(a,a-dimethylbenzyl) diphenylamine (XDPA)), phosphites (e.g., tris(2,4-di-tert-butylphenyl)phosphite), and antioxidant vitamins (e.g., ascorbic acid).
  • the compound PETC is commercially available as Irganox ® 1010 (BASF) or Dovernox ® 10 (Dover Chemical Corp.); the compound ethylenebis (oxyethylene) bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate) is commercially available as Irganox ® 245 (BASF); the compound tris(2,4-di-tert-butylphenyl)phosphite is commercially available as Irgafos ® 168 (BASF); and the compound octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)-propionate is commercially available as Irganox ® 1076 (BASF) or Dovernox ® 76 (Dover Chemical Corp.).
  • a color stabilizing step may include the use of a combination of color stabilizing additive compounds, as a color stabilizing medium, including a combination of any of the compounds and/or classes of compounds as described above, such as a combination of one or more / ⁇ ? r/-butyl- substituted phenols and one or more phosphites.
  • a combination of 50 wt-% PETC and 50 wt-% tris(2,4-di-tert-butylphenyl)phosphite is commercially available as Irganox ® B255 (BASF).
  • the combination of 20 wt-% octadecyl-3-(3,5-di-tert- butyl-4-hydroxyphenyl)-propionate and 80 wt-% tris(2,4-di-tert-butylphenyl)phosphite is commercially available as Irganox ® B900 (BASF).
  • the combination of 50 wt-% PETC and 50 wt-% tris(2,4-di-tert-butylphenyl)phosphite is commercially available as Irganox ® B225 (BASF).
  • One or more color stabilizing additive compounds may be present in products such as (i) a mixed monomer composition comprising two monomers, or (ii) a separated fraction thereof that may be enriched in a given monomer (relative to the mixed monomer composition), (iii) an esterified mixed monomer composition comprising two ester derivatives of two monomers, (iv) a separated fraction thereof that may be enriched in a given ester derivative of a monomer (relative to the esterified mixed monomer composition), or (v) a bio-based polymer as described herein.
  • Such bio-based polymer may have both furandicarboxylate moieties and terephthalate moieties, or otherwise may have all or substantially all furandicarboxylate moieties, or all or substantially all terephthalate moieties.
  • the amount, or combined amount in the case of a combination may be generally from 10 wt-ppm to 1 wt-%, typically from 50 wt-ppm to 2000 wt-ppm, and often from 50 wt-ppm to 1500 wt-ppm.
  • the additive BHA may be present in any such product (e.g., comprising both FDCA and TPA to stabilize these monomers) in an amount from 100 wt-ppm to 500 wt-ppm, or the additive Irganox ® 245 may be present in any such product (e.g., comprising both FDCA and TPA to stabilize these monomers) in an amount from 800 wt-ppm to 1200 wt-ppm.
  • the additive BHA may be present in any such product (e.g., comprising both FDCA and TPA to stabilize these monomers) in an amount from 800 wt-ppm to 1200 wt-ppm.
  • any “stabilized, esterified” composition (stabilized, esterified mixed monomer composition) comprising two ester derivative monomers (e.g., both FDME and DMT), or any “stabilized, esterified” fraction enriched in a given ester derivative monomer (e.g., FDME or DMT), as described herein, can be equivalently, (i) in the case of omitting the color stabilizing step, an “esterified” mixed monomer composition comprising two ester derivative monomers (e.g., both FDME and DMT), or an “esterified” fraction enriched in a given ester derivative monomer (e.g., FDME or DMT), or (ii) in the case of omitting the esterifying step, a “stabilized” mixed monomer composition comprising two ester derivative monomers (e.g., both FDME and DMT), or an “esterified” fraction enriched in a given ester derivative monomer (e.g., FDME or DMT), or
  • a “stabilized, esterified” composition (stabilized, esterified mixed monomer composition) comprising two ester derivative monomers (e.g., both FDME and DMT), or a “stabilized, esterified” fraction enriched in a given ester derivative monomer (e.g., FDME or DMT)
  • first color stabilizing and then esterifying by first esterifying and then color stabilizing, or by performing both steps simultaneously (e.g., by contacting an esterification reaction mixture with a color stabilizing medium as described herein).
  • Steps of esterifying monomers such as FDCA and TPA, for forming ester derivatives comprise reacting these monomers with an esterifying agent such as an alcohol, for example methanol if a dimethyl ester is desired or ethanol if an diethyl ester is desired, or possibly phenol, if a diphenyl ester is desired.
  • an esterifying agent such as an alcohol, for example methanol if a dimethyl ester is desired or ethanol if an diethyl ester is desired, or possibly phenol, if a diphenyl ester is desired.
  • the reaction of FDCA and/or TPA, or other monomer(s), with the appropriate alcohol, or phenol may be carried out in an esterification reaction mixture including a high boiling point solvent (e.g., dimethyl sulfoxide, dimethylacetamide, sulfolane, FDME, g-butyrolactone, isosorbide or its dimethyl ether, propylene carbonate, adipic acid, isophorone, ethyl phenyl ether, diphenyl ether, dibenzyl ether, aromatic 200 fluid, butyl phenyl ether, methyl heptyl ketone, ethyl phenyl ketone, 2’-hydroxyacetophenone, decahydronaphthalene, tetrahydronaphthalene, etc.) under suitable esterification conditions.
  • a high boiling point solvent e.g., dimethyl sulfoxide, dimethylacetamide, sulfolane, FDME
  • esterification reaction may be performed together with distillation (according to a reactive distillation process) for separation of the FDME, DMT, or other ester derivative.
  • a step of esterifying comprises reacting any such mixed monomer composition or separated fraction thereof with methanol as the esterifying agent.
  • esterifying such mixed monomer composition may comprise reacting it with methanol to provide an esterified mixed monomer composition (or stabilized esterified mixed monomer composition) comprising FDME and DMT.
  • esterification of a mixed monomer composition or stabilized composition is desirable as the ester derivative monomers, e.g., FDME and DMT have lower boiling points relative to their parent dicarboxylic acid compounds, and are more amenable to separation by distillation in view of this and their relative volatilities.
  • step(s) of esterifying as described herein generally and/or with respect to the embodiments illustrated in the figures, it is possible that further, downstream step(s) may be used to convert the ester derivative(s) (e.g., FDME and/or DMT) obtained from the esterifying step back to the parent, carboxylic acid(s) (e.g., FDCA and/or TPA), for example prior to polymer forming step(s) as described herein.
  • ester derivative(s) e.g., FDME and/or DMT
  • carboxylic acid(s) e.g., FDCA and/or TPA
  • representative mixed monomer compositions may comprise, as color-forming byproducts, an aldehyde derivative of FDCA (e.g., FFCA) and an aldehyde derivative of TPA (e.g., 4-CBA), and processes may comprise selectively hydrogenating one or both of the aldehyde derivative of FDCA and the aldehyde derivative of TPA (e.g., reduce their concentrations in a given process stream to improve color and/or color stability of a copolymer ultimately produced from that process stream).
  • FDCA e.g., FFCA
  • TPA e.g., 4-CBA
  • This step of selectively hydrogenating one or both of the aldehyde derivative of FDCA and the aldehyde derivative of TPA may occur following a separation of the mixed monomer composition into an FDCA-enriched fraction and a TPA-enriched fraction.
  • processes may further comprise, in a step of esterifying one or both of the FDCA and TPA, producing, as further color- forming byproducts, one or both of an aldehyde derivative of an ester derivative of FDCA (e.g., FFME) and an aldehyde derivative of an ester derivative of TPA (e.g., 4-CME).
  • Representative processes in this case may further comprise selectively hydrogenating one or both of the aldehyde derivative of the ester derivative of FDCA and the aldehyde derivative of the ester derivative of TPA (e.g., reduce their concentrations in a given process stream to improve color and/or color stability of a copolymer ultimately produced from that process stream).
  • this may comprise esterifying these materials concurrently in the mixed monomer composition by reaction with an esterifying agent in the presence or absence of a suitable esterification catalyst, to provide an esterified mixed monomer composition comprising both the aldehyde derivative of the ester derivative of FDCA and the aldehyde derivative of the ester derivative of TPA.
  • Esterifying both of the FDCA and TPA may occur upstream of a separation of the esterified mixed monomer composition into a first fraction enriched in an ester derivative of FDCA and a second fraction enriched in an ester derivative of TPA.
  • this may comprise esterifying one or both of an FDCA-enriched fraction and a TPA- enriched fraction, by reaction with an esterifying agent, downstream of a separation of the mixed monomer composition into the FDCA-enriched fraction and the TPA-enriched fraction.
  • any of the mixed monomer oxidation products e.g. , comprising both FDCA and TP A
  • separated fractions thereof e.g. , enriched in FDCA or enriched in TP A, relative to the mixed monomer oxidation products from which the fractions derive
  • esterified mixed monomer compositions e.g., comprising both FDME and DMT
  • separated fractions thereof e.g., enriched in FDME or enriched in DMT, relative to the esterified mixed monomer oxidation products from which the fractions derive
  • optionally having been subjected to a color stabilizing step may be used for forming polymers.
  • Forming a polymer from a combined monomer oxidation product directly can yield a copolymer having both FDCA-related moieties (e.g., furandicarboxylate moieties) and TPA-related moieties (e.g., terephthalate moieties), whereas forming a polymer from a separated fraction thereof can yield a copolymer having FDCA-related moieties and being substantially free of (or at least having less of) TPA-related moieties (e.g., providing a substantially bio-based copolymer wherein the p-xylene is conventionally petroleum-based), or otherwise a copolymer having TPA-related moieties and being substantially free of (or at least having less of) FDCA-related moieties (which might be desirable for some practitioners given the well-established infrastructure for recycling PET and in consideration of the difficulty of converting users to a new polymer).
  • FDCA-related moieties e.g., furandicarboxylate moi
  • representative polymer forming steps can include, for the production of polyesters, (A)(i) esterifying a mixed monomer composition or separated fraction thereof, as described herein, or (A)(ii) transesterifying an esterified mixed monomer composition or separated fraction thereof, as described herein, and (B) polymerizing by polycondensation.
  • polyester polymer forming steps involve the polymerization of monomers and ester derivative monomers described herein, and particularly the monomers FDCA and/or TPA and the ester derivative monomers FDME and/or DMT, with suitable co monomers such as diols.
  • suitable co monomers such as diols.
  • ethylene glycol may be used as the co-monomer to produce PEF (from FDCA or FDME) or PET (from TPA or DMT).
  • the co-monomer 1,3- propanediol may be used to produce poly(trimethylene furan dicarboxylate) (PTF) (from FDCA or FDME) or polypropylene terephthalate (from TPA or DMT).
  • Particular methods may comprise producing a precursor composition comprising a prepolymer that is an esterified intermediate such as the reaction product of FDCA and/or TPA with the co-monomer, or a transesterified intermediate such as the reaction product of FDME and/or DMT with the co-monomer.
  • a precursor composition comprising a prepolymer that is an esterified intermediate such as the reaction product of FDCA and/or TPA with the co-monomer, or a transesterified intermediate such as the reaction product of FDME and/or DMT with the co-monomer.
  • the prepolymer whether an esterified intermediate or transesterified intermediate, is functionalized with terminal alcohol groups (e.g., rather than terminal carboxylate groups of TPA, or terminal methyl groups of FDME or DMT) and therefore may then be subjected to polycondensation to provide a copolymer as described herein, and particularly a poly(alkylene furan dicarboxylate) polymer, a poly(alkylene terephthalate) polymer, or a copolymer comprising both alkylene furan dicarboxylate residues and alkylene terephthalate (or alkylene terephthalate) residues.
  • terminal alcohol groups e.g., rather than terminal carboxylate groups of TPA, or terminal methyl groups of FDME or DMT
  • aldehyde derivatives described herein present in monomer compositions (e.g., FFCA in an FDCA monomer composition, 4-CBA in a TPA monomer composition, FFME in an FDME monomer composition, or 4-CME in a DMT monomer composition) that are used to produce precursor compositions, will become esterified or transesterified, under conditions used to produce the precursor composition.
  • monomer compositions e.g., FFCA in an FDCA monomer composition, 4-CBA in a TPA monomer composition, FFME in an FDME monomer composition, or 4-CME in a DMT monomer composition
  • Processes for producing a polyester polymer can therefore include both a first, esterification or transesterification step to produce an intermediate (prepolymer), followed by a second, polycondensation step.
  • the first step may be catalyzed by an esterification/transesterification catalyst at a temperature from 150°C (302°F) to 250°C (482°F), and carried out until the concentration of the starting monomer(s) or ester derivative monomer(s) is reduced to less than 3 mol-%.
  • the catalyst may comprise an organotin(IV) compound, present in a concentration from 0.01 mol-% to 0.2 mol-% in a polymer forming reaction mixture, relative to the starting monomer(s) or ester derivative(s).
  • the prepolymer, as described herein, may therefore be the reaction product of two diol monomers and one monomer bearing either a furandicarboxylate moiety or a terephthalate (benzenecarboxylate) moiety that is ultimately present in the backbone of the resulting polymer.
  • diols of interest for forming the intermediate (prepolymer) include those, like FDCA, which may be bio-derived, such as in the case of isohexides. These compounds are bicyclic, rigid diols that differ only in the orientation of the hydroxyl groups at C2 and C5 ring positions, and they can be obtained by cyclodehydration of hexitols.
  • isomannide can be obtained (endo-endo) from mannitol
  • isosorbide (exo-endo) can be obtained from sorbitol
  • isoidide (exo-exo) can be obtained from iditol.
  • the intermediate (prepolymer) that is formed may optionally be isolated from the reaction mixture of the first reaction step, although generally this is not necessary.
  • the second step of poly condensation may be catalyzed and performed under reduced pressure (e.g., 100 Pascals (Pa) or less), at a temperature in the range of the melting point of the resulting copolymer to 30°C (54°F) above this temperature, and preferably at a temperature of at least 180°C (356°F).
  • the poly condensation catalyst may comprise a tin(II) compound, such as tin(II) oxide or an organotin(II) compound.
  • a catalyst based on titanium may be employed, such as titanium or a chelated titanium compound, having various ligands that can include alkoxides, for example propoxide or ieri-butoxide.
  • Representative catalysts are therefore titanium (IV) propoxide and titanium (IV) ieri-butoxide.
  • FDCA and/or TPA may be used in forming polymers other than polyester polymers.
  • polyamide polymers may be formed in the case of reacting one or both of FDCA and TPA, separately or in combination, with a co-monomer having at least two amino groups (e.g. , a diamine), to produce a polyamide having one or both of FDCA- related moieties and TPA-related moieties.
  • Suitable co-monomers include aliphatic diamines such as hexamethylene diamine and aromatic diamines such as paraphenylene diamine.
  • polyester polymers may be formed in the case of reacting, as a co-monomer, a hydroxyl (alcohol) derivative of one or both of FDCA and TPA (e.g., a diol derivative of one or both of FDCA and TPA), separately or in combination, with a poly acid (e.g., FDCA or TPA) or its ester derivative thereof to produce a polyester having one or both of FDCA-related moieties and TPA-related moieties.
  • a hydroxyl (alcohol) derivative of one or both of FDCA and TPA e.g., a diol derivative of one or both of FDCA and TPA
  • a poly acid e.g., FDCA or TPA
  • Suitable co-monomers that are hydroxyl derivatives of FDCA include furan 2,5-diol and furan 2,5-dimethanol, and suitable co monomers that are hydroxyl derivatives of TPA include hydroquinone and benzene 1,4- dimethanol.
  • a derivative of FDCA and/or a derivative of TPA may be used in forming polymers other than polyester polymers.
  • polyurethane polymers may be formed in the case of reacting, as a co-monomer, a hydroxyl (alcohol) derivative of one or both of FDCA and TPA (e.g. , a diol derivative of one or both of FDCA and TPA), separately or in combination, with a polyisocyanate to produce a polyurethane having one or both of FDCA- related moieties and TPA-related moieties.
  • Suitable co-monomers that are hydroxyl derivatives of FDCA include those described above with respect to the formation of polyester polymers.
  • Suitable polyisocyanates include diisocyanates, and in particular aromatic diisocyanates such as toluene diisocyanate, methylene diphenyl diisocyanate, and polymeric methylene diisocyanates.
  • polyamide polymers may be formed in the case of reacting, as a co-monomer, an amino derivative of one or both of FDCA and TPA (e.g.
  • a diamino derivative of one or both of FDCA and TPA separately or in combination, with a poly acid (e.g., FDCA or TPA) to produce a polyamide having one or both of FDCA-related moieties and TPA-related moieties.
  • Suitable co-monomers that are amino derivatives of FDCA include furan 2,5-diamine and furan 2,5-dialkyl amines such as furan 2,5-dimethanamine
  • suitable co-monomers that are amino derivatives of TPA include benzene 1,4-diamine and benzene 1,4 dialkylamines such as benzene 1 ,4-dimethanamine.
  • polyamide polymers may be formed in the case of reacting an acyl derivative of one or both of FDCA and TPA (e.g. , a diacyl chloride derivative of one or both of FDCA and TPA), separately or in combination, with a co-monomer having at least two amino groups (e.g., a diamine), to produce a polyamide having one or both of FDCA-related moieties and TPA-related moieties.
  • a co-monomer having at least two amino groups e.g., a diamine
  • Suitable acyl derivatives of FDCA include furan 2,5-diformyl chloride and furan 2,5-dialkyl chlorides such as furan 2,5-diacetyl chloride
  • suitable acyl derivatives of TPA include benzene 1,4-diformyl chloride and benzene 1,4 dialkyl chlorides such as benzene 1,4- diacetylchloride.
  • Suitable co-monomers include aliphatic diamines such as hexamethylene diamine and aromatic diamines such as paraphenylene diamine.
  • polyurethane polymers may be formed in the case of reacting an isocyanate derivative of one or both of FDCA and TPA (e.g.
  • a diisocyanate derivative of one or both of FDCA and TPA separately or in combination, with a co-monomer having at least two hydroxyl groups (e.g., a diol), to produce a polyurethane having one or both of FDCA-related moieties and TPA-related moieties.
  • Suitable isocyanate derivatives of FDCA include furan 2,5-diisocyanate and furan 2,5-dialkyl isocyanates such as furan 2,5-dimethanisocyanate
  • suitable isocyanate derivatives of TPA include benzene 1 ,4-diisocyanate and benzene 1 ,4 dialkyl isocyanates such as benzene 1,4-dimethanisocyanate.
  • Suitable co-monomers include diols such as those described above for forming an intermediate (prepolymer) used to ultimately produce a polyester polymer.
  • polycarbonate polymers may be formed in the case of reacting a hydroxyl (alcohol) derivative of one or both of FDCA and TPA (e.g., a diol derivative of one or both of FDCA and TPA), separately or in combination, with phosgene to produce a polycarbonate having one or both of FDCA-related moieties and TPA-related moieties.
  • a hydroxyl (alcohol) derivative of one or both of FDCA and TPA e.g., a diol derivative of one or both of FDCA and TPA
  • Suitable hydroxyl derivatives of FDCA include those described above with respect to co-monomers the formation of polyester polymers.
  • the process illustrated in FIG. 1 comprises steps for making a mixed monomer composition comprising FDCA and TPA as described above, including steps of dehydrating 100, oxidizing 200, optional color stabilizing 50, optional esterifying 55, and polymer forming 300.
  • dehydration feed 10 comprising one or more carbohydrates having a six-carbon sugar unit is subjected to dehydrating 100 to provide dehydration product 12, all or a portion of which may be used as a component of the oxidation feed.
  • a contaminant portion of dehydration product 12 such as a portion 11 that is concentrated in humins (e.g., in a filtration retentate) may be removed in order to provide purified portion 12' of dehydration product 12 that may be used as a component of, or possibly the entire, the oxidation feed.
  • the depicted process may comprise contacting dehydration product 12 or purified portion 12' thereof in the presence of oxygen, such as introduced in oxygen-containing feed 16 (e.g., air), with an oxidation catalyst.
  • a second component of the oxidation feed, in addition to dehydration product 12 or purified portion 12' thereof, is para-xylene-containing feed 14.
  • Mixed monomer composition 18 comprising (i) FDCA from the oxidation of dehydration product 12 or purified portion 12' thereof, and (ii) TPA from the oxidation of para-xylene, is withdrawn from oxidizing step 200 (e.g., an oxidation reactor). All or a portion of the mixed monomer composition (or oxidation product) 18 may be used in polymer forming step 300, optionally following color stabilizing 50 to provide a stabilized composition 20 and/or esterifying 55, for example to provide a stabilized, esterified composition 22 (if both steps are used). As described herein, these optional steps may be performed in either order.
  • Mixed monomer composition 18 may be obtained from oxidizing step 200, for example in an effluent of an oxidation reactor, from which a solvent recycle 15 is separated (e.g. , based on a relative insolubility, of monomers in mixed monomer composition 18, in a solvent or solvent system for FDCA-forming furanics in dehydration product 12). All or a portion of solvent recycle 15 may be fed back or returned to dehydrating 100 step (e.g., a dehydration reactor), and a fresh, makeup portion 17 of solvent may be added to solvent recycle 15 or otherwise directly to dehydrating 100 step.
  • dehydrating 100 step e.g., a dehydration reactor
  • all or a portion of the para- xylene added to the downstream oxidizing 200 step may be present in dehydration product 12 or purified portion 12' thereof.
  • para- xylene-containing feed 14 may represent a second portion that is added directly to oxidizing 200 step (e.g., oxidation reactor)
  • fresh, makeup portion 17 of solvent may represent a fresh, makeup portion of para-xylene that is added to solvent recycle 15 or otherwise directly to dehydrating 100 step (e.g., dehydration reactor).
  • the para- xylene present in dehydration product 12 may represent a combined amount of fresh, makeup portion 17 and an amount present in solvent recycle 15 (e.g., at steady-state operation).
  • solvent recycle 15 e.g., at steady-state operation.
  • Representative processes may comprise (A) color stabilizing 50 the mixed monomer composition (or oxidation product) 18 by adding (or contacting with) color stabilizing medium 19, to provide a stabilized composition 20 comprising FDCA and TPA; and (B) optionally following (A), esterifying 55 the stabilized composition 20 by reaction with esterifying agent 21, to provide a stabilized, esterified composition 22 comprising ester derivatives of FDCA and TPA (e.g., the diesters FDME and DMT).
  • A color stabilizing 50 the mixed monomer composition (or oxidation product) 18 by adding (or contacting with) color stabilizing medium 19, to provide a stabilized composition 20 comprising FDCA and TPA
  • esterifying 55 the stabilized composition 20 by reaction with esterifying agent 21, to provide a stabilized, esterified composition 22 comprising ester derivatives of FDCA and TPA (e.g., the diesters FDME and DMT).
  • the process may for the purpose of making a copolyester from FDCA and TPA further comprise reacting stabilized composition 20 comprising FDCA and TPA with a co-monomer 24 having at least two hydroxyl groups (e.g., a diol) to produce a stabilized, co-esterified intermediate (prepolymer) composition comprising (i) a first esterified intermediate that is a reaction product of FDCA and the co monomer and (ii) a second esterified intermediate that is a reaction product of TPA and the co monomer, and polymerizing the stabilized, co-esterified intermediate composition by poly condensation of the first and second esterified intermediates to yield copolymer product 26 comprising a copolymer having furandicarboxylate moieties and terephthalate moieties.
  • a co-monomer 24 having at least two hydroxyl groups
  • the steps of reacting with co-monomer 24, followed by polymerizing by poly condensation are sub-steps of polymer forming 300.
  • the process may further comprise reacting a stabilized, esterified composition 22 comprising the ester derivatives of FDCA and TPA with co-monomer 24 having at least two hydroxyl groups (e.g., a diol) to produce a stabilized, co- transesterified intermediate (prepolymer) composition comprising (i) a first transesterified intermediate that is a reaction product of the ester derivative of FDCA and co-monomer 24 and (ii) a second transesterified intermediate that is a reaction product of the ester derivative of TPA and co-monomer 24, and polymerizing the stabilized, co-transesterified intermediate composition by polycondensation of the first and second transesterified intermediates to yield copolymer product 26 comprising a copolymer having furandicarboxylate moieties and terephthalate moieties.
  • the process may comprise (A) esterifying the mixed monomer composition 18 by reaction with esterifying agent 21, to provide an esterified mixed monomer composition comprising ester derivatives of both FDCA and TPA, and (B) optionally following (A), color stabilizing the esterified mixed monomer composition (or mixed ester composition) by adding color stabilizing medium 19 to provide a stabilized composition 22 comprising stabilized ester derivatives of both FDCA and TPA.
  • the process may, for purposes of preparing a copolyester, further comprise reacting the esterified mixed monomer composition comprising ester derivatives of both FDCA and TPA with a co-monomer 24 having at least two hydroxyl groups (e.g., a diol) to produce a co-transesterified intermediate (prepolymer) composition comprising (i) a first transesterified intermediate that is a reaction product of an ester derivative of FDCA and the co-monomer and (ii) a second transesterified intermediate that is a reaction product of an ester derivative of TPA and the co-monomer, and polymerizing the co- transesterified intermediate composition by polycondensation of the first and second esterified intermediates to yield copolymer product 26 comprising a copolymer having furandicarboxylate moieties and terephthalate moieties.
  • a co-monomer 24 having at least two hydroxyl groups (e.g., a dio
  • the steps of reacting with co monomer 24, followed by polymerizing by polycondensation are sub-steps of polymer forming 300.
  • the process may further comprise reacting the stabilized, esterified composition 22 comprising ester derivatives of both FDCA and TPA with co-monomer 24 having at least two hydroxyl groups (e.g., a diol) to produce a stabilized, co-transesterified intermediate (prepolymer) composition comprising (i) a first transesterified intermediate that is a reaction product of an ester derivative of FDCA and the co-monomer and (ii) a second transesterified intermediate that is a reaction product of an ester derivative of TPA and the co monomer, and polymerizing the stabilized, co-transesterified intermediate composition by poly condensation of the first and second transesterified intermediates to yield copolymer product 26 comprising a copolymer having furandicarboxylate moieties and terephthalate moieties.
  • the process illustrated in FIG. 2 comprises steps as illustrated in FIG. 1 for making a mixed monomer composition or co-product comprising FDCA and TPA, including steps of dehydrating 100, oxidizing 200, optional color stabilizing 50, and optional esterifying 55.
  • all or a portion of the mixed monomer composition 18, optionally stabilized composition 20, or optionally stabilized, esterified composition 22 is used in a step of separating 60, for example to provide fractions that may be enriched in one monomer or relative to another monomer, or ester derivatives of one monomer relative to the ester derivatives of the other monomer.
  • the characteristic of being “enriched in” refers to having a higher concentration of a given monomer or the ester derivatives of that monomer, relative to the product before undergoing separation.
  • a fraction that is enriched in a given monomer or the ester derivatives of that monomer e.g., FDCA, TPA, the mono- and diester derivatives of FDCA and the mono- and diester derivatives of TPA
  • a fraction being enriched in a given monomer or the ester derivatives of a given monomer may therefore also be “depleted in” (have a lower concentration of) a given monomer or the ester derivatives of a given monomer that is also present in the product before undergoing separation.
  • an FDCA-enriched fraction may be depleted in TPA, such that this fraction may be substantially free of TPA (e.g., may comprise less than 5 wt-%, less than 3 wt-%, or less than 1 wt-%) of this compound.
  • a TPA-enriched fraction may be depleted in FDCA, such that this fraction may be substantially free of FDCA (e.g., may comprise less than 5 wt-%, less than 3 wt-%, or less than 1 wt-%) of this compound.
  • a fraction enriched in the ester derivatives of FDCA (or an esterified FDCA-enriched fraction) may be depleted in the ester derivatives of TPA, such that the fraction may be substantially free of these mono- and diester derivatives (e.g., may comprise less than 5 wt-%, less than 3 wt-%, or less than 1 wt-%) of the ester derivatives of TPA.
  • a fraction enriched in the ester derivatives of TPA may be depleted in the ester derivatives of FDCA such that the fraction may be substantially free of these ester derivatives (e.g., may comprise less than 5 wt-%, less than 3 wt-%, or less than 1 wt-%) of the mono- and diester derivatives of FDCA.
  • the step of separating 60 may be performed according to any of a number of techniques, such as fractional solidification (based on melting point difference); crystallization, optionally following extraction in aqueous or organic media (based on solubility difference); adsorbent or chromatographic methods, including simulated moving bed (SMB) chromatography (based on molecular size/structure difference); and distillation, optionally with a stripping gas or extracting solvent (based on relative volatility difference).
  • a step of esterifying 55 renders the resulting ester derivative monomers more amenable to separation by distillation.
  • separating 60 may include the distillation of the esterified mixed monomer composition (or esterified oxidation product) 22 (optionally following a color stabilizing step 50) into a first fraction 251 enriched in the ester derivatives of FDCA (e.g. , FDME) and a second fraction 252 enriched in the ester derivatives of TP A (e.g., DMT).
  • the step of separating 60 may be used to separate mixed monomer composition 18 (optionally following color stabilizing 50) into a first, FDCA-enriched fraction 251 and a second, TPA-enriched fraction 252.
  • optional steps of color stabilizing 501/502, optional steps of esterifying 551/552, and steps of polymer forming 301/302 may be performed on the separated fractions, in the manner described above.
  • processes may further comprise (A) color stabilizing a first, FDCA-enriched fraction 251 by adding color stabilizing medium 19 to provide a stabilized FDCA-enriched fraction 201, and (B) optionally following (A), esterifying the stabilized FDCA-enriched fraction 201 by reaction with esterifying agent 21, to provide a stabilized, esterified FDCA-enriched fraction 221 comprising an ester derivative of FDCA.
  • the process may further comprise reacting the stabilized FDCA-enriched fraction 201 with co-monomer 24 having at least two hydroxyl groups (e.g., a diol) to produce a stabilized, esterified intermediate (prepolymer) composition comprising (i) a first esterified intermediate that is a reaction product of FDCA and the co monomer and being substantially free of (ii) a second esterified intermediate that is a reaction product of TPA and the co-monomer, and polymerizing the stabilized, esterified intermediate composition by polycondensation of the first esterified intermediate to yield a polymer product 261 comprising a polyester having furandicarboxylate moieties and being substantially free of terephthalate moieties.
  • co-monomer 24 having at least two hydroxyl groups
  • the steps of reacting with co-monomer 24, followed by polymerizing by poly condensation are sub-steps of polymer forming 301.
  • the process may further comprise reacting the stabilized, esterified FDCA-enriched fraction 221 comprising an ester derivative of FDCA (especially the diester) with co-monomer 24 having at least two hydroxyl groups (e.g., a diol) to produce a stabilized, transesterified intermediate (prepolymer) composition comprising (i) a first transesterified intermediate that is a reaction product of a mono- and/or diester derivative of FDCA and the co-monomer and being substantially free of (ii) a second transesterified intermediate that is a reaction product of an ester derivative of TPA and the co-monomer, and polymerizing the stabilized, transesterified intermediate composition by polycondensation of the first transesterified intermediate to yield polyester product 261 comprising a polyester having furandicarboxylate moieties and being substantially free
  • processes may further comprise (A) esterifying a first, FDCA-enriched fraction 251 by reaction with an esterifying agent 21, to provide an esterified FDCA-enriched fraction comprising an ester derivative of FDCA, and (B) optionally following (A), color stabilizing the esterified FDCA-enriched fraction by adding color stabilizing medium 19, to provide a stabilized, esterified FDCA- enriched fraction 221.
  • the processes may further comprise reacting the esterified FDCA-enriched fraction comprising an ester derivative of FDCA with a co-monomer 24 having at least two hydroxyl groups (e.g., a diol) to produce a transesterified intermediate (prepolymer) composition comprising (i) a first transesterified intermediate that is a reaction product of a mono- and/or diester derivative of FDCA and the co-monomer and being substantially free of (ii) a second transesterified intermediate that is a reaction product of an ester derivative of TPA and the co-monomer, and polymerizing the transesterified intermediate composition by polycondensation of the first transesterified intermediate to yield copolymer product 261 comprising a copolymer having furandicarboxylate moieties and being substantially free of terephthalate moieties.
  • a transesterified intermediate prepolymer composition
  • a first transesterified intermediate that is a reaction product of a mono-
  • the steps of reacting with co-monomer 24, followed by polymerizing by polycondensation, are sub-steps of polymer forming 300.
  • the processes may further comprise reacting a stabilized, esterified FDCA- enriched fraction 221 with a co-monomer 24 having at least two hydroxyl groups (e.g.
  • a diol to produce a stabilized, transesterified intermediate (prepolymer) composition
  • a stabilized, transesterified intermediate (prepolymer) composition comprising (i) a first transesterified intermediate that is a reaction product of a mono- or diester derivative of FDCA and the co-monomer and being substantially free of (ii) a second transesterified intermediate that is a reaction product of an ester derivative of TPA and the co-monomer, and polymerizing the stabilized, transesterified intermediate composition by polycondensation of the first transesterified intermediate to yield a copolymer product comprising a copolymer having furandicarboxylate moieties and being substantially free of terephthalate moieties.
  • the steps of reacting with co-monomer 24, followed by polymerizing by polycondensation are sub steps of polymer forming 301.
  • processes may further comprise (A) color stabilizing a second, TPA-enriched fraction 252 by adding color stabilizing medium 19, to provide a stabilized TPA-enriched fraction 202; and (B) optionally following (A), esterifying the stabilized TPA-enriched fraction 202 by reaction with esterifying agent 21, to provide a stabilized, esterified TPA-enriched fraction 222 comprising an ester derivative of TPA.
  • the processes may further comprise reacting the stabilized TPA-enriched fraction 202 with co-monomer 24 having at least two hydroxyl groups (e.g.
  • a diol to produce a stabilized, esterified intermediate (prepolymer) composition
  • a stabilized, esterified intermediate (prepolymer) composition comprising (i) a first esterified intermediate that is a reaction product of TPA and the co-monomer and being substantially free of (ii) a second esterified intermediate that is a reaction product of FDCA and the co-monomer, and polymerizing the stabilized, esterified intermediate composition by polycondensation of the first esterified intermediate to yield a polyester product 262 comprising a polyester having terephthalate moieties and being substantially free of furandicarboxylate moieties.
  • the steps of reacting with co-monomer 24, followed by polymerizing by polycondensation, are sub-steps of polymer forming 302.
  • the processes may further comprise reacting a stabilized, esterified TPA-enriched fraction 222 comprising an ester derivative of TPA (especially the diester) with co-monomer 24 having at least two hydroxyl groups (e.g. , a diol) to produce a stabilized, transesterified intermediate (prepolymer) composition comprising (i) a first transesterified intermediate that is a reaction product of a mono- and/or diester derivative of TPA and the co-monomer and being substantially free of (ii) a second transesterified intermediate that is a reaction product of an ester derivative of FDCA and the co-monomer, and polymerizing the stabilized, transesterified intermediate composition by polycondensation of the first transesterified intermediate to yield polyester product 262 comprising a polyester having terephthalate moieties and being substantially free of furandicarboxylate moieties.
  • the steps of reacting with co-monomer 24, followed by polymerizing by polycondensation
  • processes may further comprise (A) esterifying a second, TPA-enriched fraction 252 by reaction with esterifying agent 21, to provide an esterified TPA-enriched fraction comprising an ester derivative of TPA, and (B) optionally following (A), color stabilizing the esterified TPA-enriched fraction by adding color stabilizing medium 19, to provide a stabilized, esterified TPA-enriched fraction 222.
  • the processes may further comprise reacting the esterified TPA-enriched fraction comprising an ester derivative of TPA with co-monomer 24 having at least two hydroxyl groups (e.g., a diol) to produce a transesterified intermediate (prepolymer) composition comprising (i) a first transesterified intermediate that is a reaction product of a mono- and/or diester derivative of TPA and the co-monomer and being substantially free of (ii) a second transesterified intermediate that is a reaction product of an ester derivative of FDCA and the co-monomer, and polymerizing the transesterified intermediate composition by poly condensation of the first transesterified intermediate to yield a polyester product 262 comprising a polyester having terephthalate moieties and being substantially free of furandicarboxylate moieties.
  • a transesterified intermediate prepolymer composition
  • a first transesterified intermediate that is a reaction product of a mono- and/or diester derivative of TPA and the
  • the steps of reacting with co-monomer 24, followed by polymerizing by polycondensation are sub-steps of polymer forming 302.
  • the processes may further comprise reacting a stabilized, esterified TPA-enriched fraction 222 with co-monomer 24 having at least two hydroxyl groups (e.g., a diol) to produce a stabilized, transesterified intermediate (prepolymer) composition comprising (i) a first transesterified intermediate that is a reaction product of a mono- and/or diester derivative of TPA and the co monomer and being substantially free of (ii) a second transesterified intermediate that is a reaction product of the ester derivative of FDCA and the co-monomer, and polymerizing the stabilized, transesterified intermediate composition by poly condensation of the first transesterified intermediate to yield polyester product 262 comprising a polyester having terephthalate moieties and being substantially free of furandicarboxylate moieties.
  • FIG. 3 illustrates embodiments of the invention relating to processes for, and the resulting apparatuses/equipment obtained by, modifying (e.g., retrofitting) a monomer manufacturing facility or plant.
  • a representative TPA production plant for example, may have been previously constructed and may, for example, operate below its design capacity or be decommissioned altogether.
  • the step of modifying may be used to restore overall profitability, or may improve process economics, as a result of the added ability to co-process a second monomer-forming co-feed, and especially one that is renewably- sourced, in addition to para- xylene.
  • a TPA production plant to be modified may comprise oxidation reactor 205 configured to receive, as feeds, (i) para- xylene, such as in para- xylene-containing feed 14, as well as (ii) oxygen, such as in oxygen-containing feed 16.
  • the TPA production plant may further comprise a downstream TPA crystallization and recovery section 210 that is configured to separate and recycle solvent 45 from this section back to oxidation reactor 205.
  • Modifying may comprise retrofitting the TPA production plant with a connection to an upstream carbohydrate dehydration reactor 100, for example using an existing inlet of oxidation reactor 205, such as an inlet for the para- xylene-containing feed 14, according to the dashed arrows in FIG.
  • connection may be provided with an added inlet, according to the solid arrows in FIG. 3, connecting dehydration product 12 or purified portion 12' thereof directly to oxidation reactor 205.
  • An outlet of oxidation reactor 205 may be configured to provide (e.g., flow) oxidation effluent 18', for example comprising FDCA and TPA and/or other monomers, to the TPA crystallization and recovery section 210 that, following the retrofitting, may be configured to provide (e.g., flow) a mixed monomer composition 18 as heretofore described, having a reduced amount of solvent relative to effluent 18' or being substantially free of solvent. Modifying may further comprise configuring the TPA production plant to provide (e.g., flow or recycle) solvent 45 or at least a portion 45' thereof, back to dehydration reactor 100.
  • the salts may be employed in their hydrated, semi-hydrated or non-hydrated form when forming the metal-containing catalysts.
  • the form of cobalt(II) acetate used in making the metal-containing catalysts used in the process of the invention may be Co(OAc)2 (non-hydrated), Co(OAc)2,.xH20 (semi-hydrate), Co(OAc)2.4H20 (hydrate).
  • cobalt(II) salts that may be employed such as, for example, cobalt(II) bromide, cobalt(II) oxalate, and other cobalt(II) salts known to the skilled person for use in such oxidation processes.
  • the form of manganese(II) acetate used in making the metal-containing catalysts used in the process of the invention may be Mn(OAc)2 (non- hydrated), Mn(0Ac)2,.xH20 (semi -hydrate), Mn(0Ac)2.4H20 (hydrate).
  • Mn(OAc)2 non- hydrated
  • Mn(0Ac)2,.xH20 sini -hydrate
  • Mn(0Ac)2.4H20 hydrate
  • additional metal species present in the metal-containing catalysts e.g. for cerium(III) acetate, zirconium(IV) acetate, etc.
  • acetoxymethyl)furfural (acetoxymethyl)furfural (AcMF), and HMF dimer, representative of products obtained from the dehydration of fructose in the presence of an acetic acid and water solvent system.
  • the dehydration product used in each experiment contained 8.5 wt-% of these compounds, in solution with this solvent system.
  • An oxidation reactor used for the experiments was charged in each case with a homogeneous catalyst composition comprising cobalt, manganese, and bromine at concentrations of 4740 wt-ppm, 885 wt-ppm, and 1475 wt-ppm, respectively.
  • Oxidation reaction conditions included a temperature of 180°C and a total pressure of 15.2 bar (220 psi, 1.52 MPa), with feed rates of the dehydration product and air to the oxidation reactor being maintained at 0.9 milliliters per minute (ml/min) and 550 standard cubic centimeters per minute (seem), for a target reaction time of 60 minutes.
  • This target reaction time was namely a maximum time over which the reaction in each experiment was performed, with the possibility for shorter reaction times to result in cases of loss of “light off,” as indicated by a drop in oxygen consumption.
  • BPR back pressure regulator
  • the furan feed used in the above procedure was prepared by slightly modifying the crude liquid product from a fructose dehydration reaction. Specifically, a mixture of 19 wt.% fructose, 0.6 wt.% glucose, 7.7 wt.% water and 2 mol% HBr (relative to total sugar) in acetic acid was fed to a continuous reactor with an internal mid-point temperature of 160 °C with a liquid residence time of 1.695 min. System pressure was maintained with a back pressure regulator at 200 psig.(1.38 MPa, gauge). The dehydration product was collected and stored prior to use as oxidation feed.
  • the dehydration product prior to addition of additional solvent or co-feed, was analyzed as 4.77 wt% HMF, 3.89% wt% 5-(acetoxymethyl)furfural (AcMF), 0.15 wt% HMF dimer, 13.63% water, and 1542 ppm Br (as HBr) with the balance being acetic acid and other fructose dehydration byproducts.
  • a baseline experiment was performed using a feed of the dehydration product ("furan feed") free of aromatic co-feed as described above, and three (3) separate further experiments were performed using this feed but with added amounts of the co-feeds (i) para- xylene, according to Experiment A, (ii) ortho-xylene, according to Experiment B, and (iii) mixed xylenes, according to Experiment C.
  • the added amounts in each case represented approximately 40 mol-% of the combined FDCA-forming furanics.
  • the selectivity of the converted FDCA-forming furanics to FDCA was approximately 60 mol-%
  • this selectivity was increased to 65-69 mol-%.
  • each of the three co-feeds, and para-xylene and mixed xylenes in particular advantageously exhibited a stabilizing effect on the oxidation of FDCA-forming furanics to FDCA.
  • a series of experiments was performed to further demonstrate the simultaneous oxidation of p-xylene and “on path” furanics (OPF).
  • a solution of on path furanics was prepared by heating 218 gm of a mixture of 33 wt% corn syrup (containing 76.25 wt% fructose, 0.96 wt% dextrose, and 22.71 wt% water), enough water such that the total water content was 7.53 wt%, with 2.0 mol% HBr relative to total fructose and glucose and a balance of acetic acid to 155 deg. C in a 300 mL titanium reactor pressurized to 220 psig (1.52 MPa, gauge) with nitrogen. Immediately after reaching 155 deg.
  • Oxidations were conducted in a semi-batch mode using a 300 mL Ti batch reactor equipped with a gas dispersion impellor, supplied by Parr.
  • the reactor was initially charged with 75 gm of acetic acid, water, cobalt acetate tetrahydrate, manganese acetate tetrahydrate, and hydrobromic acid such that the feed composition matched the initial concentration targets listed in table 1. It was then sealed and pressurized to approximately 100 psi (0.69 MPa) nitrogen before heating to 180 °C while stirring at 1200 rpm. Pressure in the reactor was maintained with a back pressure regulator (BPR) adjusted to 220 psi (1.52 MPa).
  • BPR back pressure regulator
  • 207 g of a mixture of 33 wt% corn syrup (containing 76.25 wt% fructose, 0.96 wt% dextrose, and 22.71 wt% water), enough water such that the total water content was 7.53 wt%, 2.36 mol% HBr relative to total fructose and glucose, the specified wt% of p-xylene as in Table 2, and a balance of acetic acid to 155 deg. C in a 300 mL titanium reactor pressurized to 220 psig (1.52 MPa, gauge) with nitrogen. Immediately after reaching 155 deg. C the reaction was quenched in an ice bath to halt the reaction.
  • FIG. 4 depicts a Table.
  • OAc refers to acetate
  • acac refers to acetylacetonate
  • NHPI to N-hydroxyphthalimide
  • mol% is relative to the combined moles of HMF and p-xylene.
  • Figure 5 also depicts a Table.
  • heterogeneous catalysts were generally purchased from Johnson Matthey and are referred to by their catalog number with the exception of Au/TiO which was provided from STREM and ground into a fine powder.
  • a process for making a mixed monomer composition comprising 2,5-furan dicarboxylic acid (FDCA) and terephthalic acid (TPA), the process comprising: contacting an oxidation feed, in the presence of oxygen, with an oxidation catalyst to provide the mixed monomer composition, wherein the oxidation feed comprises (i) a dehydration product of one or more carbohydrates having a 6-carbon sugar unit, and (ii) para-xylene.
  • FDCA 2,5-furan dicarboxylic acid
  • TPA terephthalic acid
  • bromine source is selected from the group consisting of hydrogen bromide, hydrobromic acid, sodium bromide, potassium bromide, molecular bromine, benzyl bromide, tetrabromoethane, 1-alkylpyridinium bromides, and 1,3- dialkylimidazolium bromides.
  • oxidation catalyst is a homogenous oxidation catalyst. 42. The process of any of the preceding items, wherein the oxidation catalyst is a metal- containing catalyst.
  • the oxidation catalyst comprises Mn in the form of manganese(II) bromide.
  • the oxidation catalyst comprises Mn in the form of manganese(II) oxalate.
  • said at least one bromine-containing species is selected from the group consisting of inorganic bromides such as HBr; metal bromides such as lithium bromide, sodium bromide, potassium bromide, magnesium bromide, calcium bromide, cobalt bromide, and manganese bromide; organic bromides such as 5-(bromomethyl) furfural and derivatives thereof, and brominated furanic oligomers; and any combination of any thereof.
  • esterifying the stabilized composition by reacting the stabilized composition with an esterifying agent, to provide a stabilized, esterified composition comprising ester derivatives of FDCA and TPA.
  • esterifying agent is methanol and the ester derivatives of FDCA and TPA are respectively 2,5-furandicarboxylic acid, dimethyl ester (FDME) and dimethyl terephthalate (DMT).
  • (B) optionally following (A), color stabilizing the esterified FDCA-enriched fraction by adding a color stabilizing medium, to provide a stabilized, esterified FDCA-enriched fraction.
  • PETC rZ- butyl-4-hydroxyphenyl]propionate
  • TBHQ 2-ZerZ-butylhydroquinone
  • color stabilizing medium includes one or more phenyl-substituted amines (for example, 4,4'-bis(a,a- dimethylbenzyl) diphenylamine (XDPA)), one or more phosphites (for example, tris(2,4-di- tert-butylphenyl)phosphite), antioxidant vitamins (e.g., ascorbic acid), or any combination of any thereof.
  • phenyl-substituted amines for example, 4,4'-bis(a,a- dimethylbenzyl) diphenylamine (XDPA)
  • phosphites for example, tris(2,4-di- tert-butylphenyl)phosphite
  • antioxidant vitamins e.g., ascorbic acid
  • diol is selected from the group consisting of ethylene glycol, 1,3-propanol, isomannide, isosorbide, isoidide, furan-2,5-diol, furan-2,5- dimethanol, hydroquinone, benzene- 1,4-dimethanol, and any combination of any thereof.
  • a process for making a mixed monomer composition comprising 2,5-furan dicarboxylic acid (FDCA) and terephthalic acid (TPA), the process comprising: co-feeding (i) FDCA-forming furanics and (ii) para- xylene to an oxidation reactor containing an oxidation catalyst and reactant oxygen, to provide the mixed monomer composition.
  • FDCA 2,5-furan dicarboxylic acid
  • TPA terephthalic acid
  • bromine source is selected from the group consisting of inorganic bromides such as HBr; metal bromides such as lithium bromide, sodium bromide, potassium bromide, magnesium bromide, calcium bromide, cobalt bromide, and manganese bromide; organic bromides such as 5-(bromomethyl) furfural and derivatives thereof, and brominated furanic oligomers; and any combination of any thereof.
  • inorganic bromides such as HBr
  • metal bromides such as lithium bromide, sodium bromide, potassium bromide, magnesium bromide, calcium bromide, cobalt bromide, and manganese bromide
  • organic bromides such as 5-(bromomethyl) furfural and derivatives thereof, and brominated furanic oligomers; and any combination of any thereof.
  • any of items 138 to 223, wherein the mixed monomer composition comprises, as color- forming byproducts, an aldehyde derivative of FDCA and an aldehyde derivative of TPA, the process further comprising selectively hydrogenating one or both of the aldehyde derivative of FDCA and the aldehyde derivative of TPA.
  • the mixed monomer composition comprises, as color- forming byproducts, an aldehyde derivative of FDCA and an aldehyde derivative of TPA
  • the process further comprising, in a step of esterifying one or both of the FDCA and TPA, producing, as further color- forming byproducts, one or both of an aldehyde derivative of an ester derivative of FDCA and an aldehyde derivative of an ester derivative of TPA, and the process further comprising selectively hydrogenating one or both of the aldehyde derivative of the ester derivative of FDCA and the aldehyde derivative of the ester derivative of TPA.
  • bromine source is selected from the group consisting of hydrogen bromide, hydrobromic acid, sodium bromide, potassium bromide, molecular bromine, benzyl bromide, tetrabromoethane, 1-alkylpyridinium bromides, and 1,3- dialkylimidazolium bromides.
  • any of items 236 to 256, wherein said one or more carbohydrates is an aqueous fructose solution comprising from 5 wt-% to 50 wt-%, preferably from 10 wt-% to 30 wt-%, fructose based on the total weight of the solution.
  • a method for modifying a terephthalic acid (TP A) production plant comprising an oxidation reactor adapted to receive para- xylene and oxygen as feeds, and further comprising a downstream TPA crystallization and recovery section configured to separate solvent from TPA and recycle the solvent to the oxidation reactor, the method comprising retrofitting said TPA production plant with a connection from an existing inlet of the oxidation reactor, or from an added inlet of the oxidation reactor, to an upstream carbohydrate dehydration reactor.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Furan Compounds (AREA)
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Abstract

La présente invention concerne des procédés d'oxydation de produits de déshydratation de glucides, tels que des furaniques qui peuvent être oxydés en monomère d'origine biologique acide 2,5-furanedicarboxylique (FDCA), selon lesquels certaines co-charges, ayant été découvertes comme conférant un effet de stabilisation de réaction bénéfique, sont oxydées conjointement avec les produits de déshydratation de glucides. Cela peut avantageusement contrebalancer, en totalité ou en partie, les effets néfastes d'impuretés d'humine présentes dans la charge d'oxydation, de telles impuretés ayant été générées en tant que sous-produits de l'étape de déshydratation en amont. Une co-charge importante est le para-xylène, qui peut être cooxydé pour former le monomère acide téréphtalique (TPA) à base de pétrole, de sorte que le cotraitement peut avantageusement produire deux monomères de valeur, tout en améliorant les performances, en particulier en termes de stabilité de réaction, par rapport à des procédés comparables dans lesquels seul le premier monomère est produit. Des aspects apparentés impliquent des opportunités pour moderniser des installations existantes de production de monomères pour permettre le cotraitement de produits de déshydratation de glucides qui peuvent conduire aux avantages mentionnés ci-dessus.
EP21803766.1A 2020-05-15 2021-05-12 Coproduction de monomères, comprenant au moins un monomère d'origine biologique Withdrawn EP4136082A4 (fr)

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WO2013040514A1 (fr) * 2011-09-16 2013-03-21 Micromidas Inc. Procédés de fabrication de para-xylène et d'acide téréphtalique
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US9150484B2 (en) * 2011-12-29 2015-10-06 Uop Llc Process for producing terephthalic acid
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